The increase comes as the city collects 350 tonnes of mégots, as they are known in French, each year.
The Town Hall will also roll out 30,000 new ashtray bins to encourage smokers to dispose of their cigarettes properly, while 100 staff will be tasked with enforcing the rules.
About a quarter of France's population are smokers, which is on the higher end for Western Europe but lower than Spain, Greece and Eastern European nations, according to a 2012 World Health Organisation report.
The local government in Paris, meanwhile, has said that cigarette stubs take up to 12 years to disintegrate, and contains heavy metals and pollutants like nicotine and lead.
One stub can pollute more than 500 litres of water.
The decree to stiffen the fine was passed in March, and city officials handed out warnings throughout the month of September.
Mao Peninou, deputy mayor of Paris in charge of cleanliness, told RFI that the fine is necessary to prevent toxic products from filtering into the soil and air.
“Cigarette butts thrown on the ground are dirty. It's a hassle to clean, because they slip between the pavement and it prevents trees from growing,” he said in a phone interview Thursday. “And then they fall into the sewers, they pollute the water with toxic products like ammonia, benzene or even uranium.
“We need Parisians, and all those who love Paris, to lose this habit of throwing their cigarettes on the ground. It’s not something you do at home, so you should do the same in the city.”
Peninou also pointed out that the fine in London for throwing a cigarette butt on the ground is 200 euros.
“We are not the first to take this step,” he said.