The fee mirrors the Congestion Charge by applying only to the central London zone and cars operating weekdays between 7am and 6pm.
Drivers of gas- or diesel-powered vehicles that do not meet the Euro 4/IV emission standards will have to pay $13.20 per day to drive in central London during daylight hours.
Mayor Khan said Monday the charge is a response to London's poor air quality, saying that around 9,000 people in London die prematurely every year from illnesses linked to polluted air.
"With almost 10,000 Londoners dying early every year due to air pollution, tackling poor air quality is a public health emergency that requires bold action", said Mayor of London, Sadiq Khan.
The Toxicity-Charge - known as the T-Charge - is to be levied on top of the existing Congestion Charge of £11.50 for the majority of cars built before 2006.
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Mayor Sadiq Khan, who introduced the scheme, claimed London now has "the world's toughest emission standard".
The mayor said: "The shameful scale of the public health crisis London faces, with thousands of premature deaths caused by air pollution, must be addressed".
About 438 schools in London are in areas exceeding legal air quality levels, according to the London mayor's office.
The T-Charge is the first of a series of new rates being introduced in London.
"Sadiq Khan tells us he is desperate to clean up London's harmful emissions but this road tax won't make a dent", said Bailey.