Drivers of some of the oldest and most polluting vehicles will face an extra £10 charge for entering central London.
London Mayor Sadiq Khan said the "toxicity", or "T-charge", is essential as he announced his latest effort to crack down on pollution in the capital.
Vehicles will be charged if they do not meet Euro 4 emission standards, typically petrol and diesel cars registered before 2006.
Around 10,000 vehicles per weekday are expected to be charged when the charge is introduced on 23 October.
It will be imposed on top of the city's congestion charge, meaning it will cost £21.50 to drive one of the target vehicles in central London between 7am and 6pm on weekdays.
Mr Khan said: "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.
"If we don't make drastic changes now we won't be protecting the health of our families in the future."
As an example of London's pollution problems, one road in England's capital exceeded its allowed annual levels of nitrogen dioxide just five days into 2017.
Earlier this week the European Commission issued a "final warning" to the UK Government for repeated breaches of legal limits.
Pollutants - much of which come from traffic, particularly diesel vehicles - cause health problems such as asthma, heart and lung diseases and are also thought to affect children's health and development.
Air pollution is linked to 9,000 early deaths in the city each year.
Mr Khan called the T-charge the "toughest emission standard of any major city" and claimed it was overwhelmingly backed by Londoners because they wanted immediate action to tackle air pollution.
The mayor's ultimate goal is the world's first "ultra-low emission zone", which will charge more polluting cars, to come in from 2019, subjet to consultation.
Mr Khan, who last month issued the first-ever very high air pollution alert, repeated his call for the Government to bring in a national diesel scrappage fund and a new Clean Air Act.
He said the buses in the capital are being retrofitted to make them cleaner and from next year City Hall will stop buying diesel buses.
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