The new Ultra Low Emission Zone (ULEZ) has expanded to cover all London boroughs from August 29.
Motorists will be slapped with daily fees when travelling through the capital if their car is non-compliant.
It will operate 24 hours a day, seven days a week, every day, except from Christmas Day (December 25).
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The zone will charge motorists £12.50 a day if their vehicle doesn't comply with emissions standards.
London Mayor Sadiq Khan faced a number of hurdles along the way but now the expansion was launched on Tuesday.
He said while it's been a "difficult decision" during the cost of living crisis, it's a "vital one".
He said: "The evidence is quite clear in relation to the consequences of air pollution.
"It does lead to, in London, around 4,000 premature deaths a year.
"It leads to children having stunted lungs forever, adults with health issues from asthma to cancer and dementia.
"We have the ULEZ in central London and it's managed to reduce the pollutants, the toxicity by almost 50%.
"A third fewer children admitted to hospital with air pollution problems because of the ULEZ in central London.
"They've not seen the benefits of ULEZ. After today, they will."
The zone is now taken up to London borders with Buckinghamshire, Essex, Hertfordshire, Kent, Berkshire and Surrey.
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Those who drive in a newly expanded zone with a non-compliant vehicle must pay a £12.50 fee.
Drivers who fail to pay the charge risk a £180 fine, reduced to £90 if paid within 14 days.
With the launch of the new zone it caused a huge demand for drivers checking the Transport for London website.
Currently motorists face a wait of a few minutes to be able to check their vehicle.
Also councils bordering London reportedly refused to put road signs about the ULEZ.
And dozens of cameras to catch non-compliant vehicles were out of order after anti-ULEZ protesters vandalised them.
Cameras were vandalised in south and west London while other drivers taped up number plates to avoid detection.
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Simon Williams, spokesperson for the RAC told BBC: "I think the councils who are contesting or battling the Mayor of London probably need to just give in and give drivers a little bit of advance warning.
"I think people do need a good advance warning of the fact they're entering the ULEZ zone so it's time that councils stopped resisting and actually go ahead and put up the signs so everyone approaching the zone from all directions has adequate warning."
Meanwhile the Mr Khan shared a post on X, formerly known as Twitter, to inform Londoners, he said: "It's here.
"In a move that will see 5million more Londoners breathe cleaner air, the ULEZ has expanded to cover all of London today."
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