Magical Princess Holyup is Chacha's alternate persona. She is what Chacha would look like when Chacha grows up. Actually, she is only the second magical princess. The first one was Magical Princess Joan who was the one who defeated Daimaou (and then imprisoned him in the Netherworld) in his first attempt to conquer the Kingdom. She is then made into a goddess as a payment for her great deeds. Magical Princess Holyup can be brought out by the transformation sequence that Chacha, Riiya and Shiine do with the use of their medallion, bracelet and ring. The transformation sequence can be read here.
At first, the magical princess only have the Beauty Selene Arrow as her weapon, but later gets the Phoenix Sword after the arrow was proven ineffective against more powerful opponents, like Access. Seravi, after the magical princess was nearly destroyed in her battle against Argyle, saw that although her offense was good, the magical princess lacked the needed defense that might have protected her against the attacks of her enemies. And so the Bird Shield was obtained. When the portal to the Netherworld was accidentally opened up was a result of the fight for the Sacred Bird, Chacha, Riiya and Shiine were forced to give up their medallion, bracelet and ring. Since the three magical gadgets were now gone, so is the Magical Princess now finally gone from the Kingdom.
Elizabeth is the blonde doll that Seravi alway carry around. Elizabeth is Seravi's most precious doll. He talks to it like it's alive and Elizabeth talks back, although it's really just Seravi talking like a ventroliquist. So, it's actually Seravi talking to himself. Weird, huh? Elizabeth acts as his conscience, telling him the best solution to a problem. But its also Seravi's way to annoy Dorothy, insulting her though Elizabeth's voice. Then the two will have their usual violent, house-destroying fights... Ironically, Elizabeth is patterned on the young golden-haired Dorothy, the one Seravi is desperately in love with.
George is a sea creature who is in love with Marin. Marin, of course, is in love with Riiya so George's love is doomed to fail. That doesn't worry George though because no matter what, he is absolutely devoted to Marin even if he knows she don't love him back. Knowing that George would do anything for her, even give up his life for her, Marin sometimes gets George to do her bidding and like any love-struck guy would do, George would obey anything that Marin wants.
Shelly is George's sister. Seeing what Marin is doing to her brother, Shelly hates Marin and she lets it show her hate to Marin. She tries to talk some sense into George but, of course, fails since George is too much hopelessly in love with Marin to follow Shelly's advice. The pink one is Shelly and the other is George.
Like what happened to Suzu/Orin's character, Chicky's original name is Piisuke but when Cartoon Network translated ACC, they changed Piisuke's name to Chicky (which is the name I'm more familiar with and the one I'll use). Chicky is actually the magnificent Phoenix Bird who, when summoned by Magical Princess Holyup, transforms into the Phoenix Sword, Holyup's other weapon. When it's not being used to fight evil, Chicky have the form of an awfully cute, little pink bird, shaped like a small, very pink ball of feathers with legs and beak sticking out of it. Chacha found Chicky when they were looking for the Phoenix Bird, not knowing that the little bird is the one they had been looking for. Chicky can't fly at first, but with Chacha's help and because of some dire situation, it soons learns to fly. It can only say "Pii! Pii!", which is why it's original name is Piisuke. When Chacha had to give up the Magical Princess, Chicky can now never transform into the Phoenix Bird (and of course, the Phoenix Sword), except maybe when it grows up. When not with Chacha and the others, Chicky usually hangs out with Principal Urara who sort of adopts it as her pet. (Or is it the other way around?)
Although chiefly a manga character, Popy was introduced in the ACC OVA (Original Video Animation), so he have the right to be here. In the manga version, Popy is a major character, and gets to hang out (reluctantly, it seems) with Chacha, Riiya and Shiine. He is telepathic, able to read other people's mind, as well as telekinetic, able to move himself or other object. He was at first, an enemy, sent to spy the Urara Magic School by it rival school, Momiji Gakuen (literally Red Maple School), because Urara's produces more students that becomes successful that Momiji's (the rival principal's name is Momiji too) do. To cut the long story short (which is what the whole OVA is about; if you want to know the whole story read it in Hitoshi Doi's site here), Popy decides to stay in Urara's and becomes the gang's newest friend.
Sherman is a referee that specializes in magical tournaments, that is, battles for a title between two magicians. More specificially, he is the offical referee for magical tournaments for the title of the World's Greatest Magician (TM). No magician gets to be declared the World's Greatest without Sherman judging it so. It seems that Sherman had this job for a long while, (for at least 15 years or so) because he was the referee (although he looked younger) for the battle between Pontius Pikapon and Seravi for the title (although it's Dorothy who gets the title...for a while).
Kyle is a magician-in-training that is also enrolled in the Urara Magic School but in another section, Section Orange. He is in love with Yakko, but is awfully shy. He is quite content to just spy on her for a far (no wonder we only get to know him during the last few episodes of the series). But when he finally gets the guts to go to Yakko and declare his feelings for her, he was rebuffed learning that Yakko is really in love with her "Prince Seravi". Yakko told him that she would give his love a chance if he gets to become the World's Greatest Magician. In the end, it all boiled down to a magical battle between him and Seravi. Seravi, who is the rightful owner of the title, of course is no match for Kyle, although Kyle put up a good fight though.