Speaking on Radio France Inter, Francois Fillon said the state would be ready to expel any girl who wore a headscarf to a state school.
"I will personally ensure that there are no exceptions, the Republic will stand firm," Mr Fillon said.
He urged leaders of Muslim groups not to inflame and politicise the issue.
Religious symbols
France's Muslim groups, who represent some of the country's estimated five million Muslims, responded angrily when the ban on headscarves and other overt religious symbols in state schools became law in March.
Proponents of the ban on religious insignia in the classroom argue it equally applies to Jewish skullcaps and Christian crucifixes.
| I hope there will be as few expulsions as
possible Francois Fillon Education Minister |
But some Muslim groups have told girls to wear whatever they want and have pledged legal aid and private tutoring if they are expelled from school.
A small minority of Muslim groups, Mr Fillon said, were spoiling for a fight.
Detailed guidelines are being drawn up ahead of the new academic year in France, when the ban will come into force.
Mr Fillon said the day-to-day responsibility for enforcing the new regulation would lie with headmasters.
"They are the advance troops of the Republic that we want to restore," Mr Fillon said, referring to the French ideal of a state that is completely independent of religion.
France's tough stance has been bolstered by a recent European Court of Human Rights decision upholding a ban imposed by Istanbul university on a student who refused to take off her Islamic headscarf.