The Hélène Boucher high school has been a flashpoint for clashes in the French capital and was one of hundreds of schools disrupted by protests on Thursday.
Riot police gathered in side streets as students converged on the school.
Many protesters wore surgical masks or hoodies, apparently to avoid being recognised.
At least a dozen demonstrations supporting the high school students' movement were planned across France later in the day, including a rally at Place de la Bastille in Paris, where tear gas and a water cannons were fired at protesters.
Police have made more than 6600 arrests since late September when students, most of them under 18, began protesting to demand more education funding, according to the interior ministry.
The Education Ministry said 375 schools were fully or partially closed on Thursday.
While the number of school closures was down compared to Tuesday, pressure is mounting on the government of outgoing President Emmanuel Macron.
The protests against the underfunding of schools - many of them struggling with dilapidated facilities and insufficient staff - have drawn troublemakers not concerned about the aims of the protest movement as well as unions and political groups.
In a TV address, Prime Minister Sébastien Lecornu lamented the "violence, students and staff being attacked, police officers and gendarmes injured, schools set on fire or vandalised, thousands of hours of classes lost, not to mention threats and insults."
He took aim at "political leaders who use this anger to conduct their electoral battles".
France goes to the polls for a presidential election in April.
"We cannot play with the safety of France's youth," Lecornu said.
At the Lycee, 18-year-old university student Emma Khelil came to offer support to those at the barricades at her former high school.
She told the Associated Press that she is really concerned about police violence.
"We're here to defend our rights, not to lose an eye or a hand," Khelil said.
She also said that she had noticed insulation problems and water leaks in the school building and had even seen rats on occasion.
Other students confirmed that they had seen rats too.
She was not convinced by Lecornu's efforts to calm the situation.
"I don't think the movement is going to lose momentum. As long as things don't change, we're going to see the movement grow stronger, and potentially a convergence of struggles, especially with the next presidential election coming up," she said.
Not long after she spoke, police surrounded a nearby square.
The crowd surged, and tear gas was fired.
Smoke from burning rubbish nearby hung in the air at Place de la République as hundreds of high school and university students prepared to march toward Place de la Bastille, the demonstration's focal point.
Some carried signs bearing their schools' names; others held placards reading "More money for repression than for our education" and "Who protects us from the police?".
"We're here, we're demonstrating, and we won't stop. Until October, November, December if necessary. Nothing will stop us," said Sofia Ferdials, 18, a student at Paris 8 University.
Dounia Gergeon, a 39-year-old school librarian, said she joined the demonstration at Place de la Bastille because she shared students' concerns and worried about a broader crisis facing young people anxious about their futures.
At the middle and high school where she works, time was set aside for students to discuss their demands.
"They do not feel supported," she said.
"They feel cornered and forced to work under these conditions."
Authorities deployed tear gas and a water cannon at the protesters, some of whom hurled projectiles at riot police.
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