The new charge will be applied during 7am to 6pm weekday hours and comes on top of the existing congestion charge of 11.50 pounds, which has been in place since 2003.
About 438 schools in London are in areas exceeding legal air quality levels, according to the London mayor's office.
The pollution is having a significant impact on human health, with a major Lancet study revealing last week that nearly 50,000 deaths in the United Kingdom past year can be attributed to the country's toxic air.
The mayor of London on Monday announced the beginning of a new fee that drivers of older, more polluting vehicles in the city must pay.
The capital city has introduced a new £10 ($13) emission charge that affects the most polluting vehicles.
"Today marks a major milestone in this journey with the introduction of the T-Charge to encourage motorists to ditch polluting, harmful vehicles".
"It's staggering that we live in a city where the air is so toxic that many of our children are growing up with lung problems", he said in a statement.
"As mayor I am determined to take urgent action to help clean up London's lethal air".
London will impose even tighter controls with the introduction of a "Ultra Low Emission Zone" in 2019.
The total daily levy can be reduced by £1 if drivers register to pay the congestion charge automatically.
"This is about an investment in our air, it's not about making a profit".
London's new Toxicity Charge (T-Charge) is already making a difference to air quality on the streets of the capital.