Europe's biggest ultra-low emission zone, spanning about 380 square km of London, came into operation on Monday, Trend reports citing Xinhua.
Around 3.8 million people live within the zone which extends to the north and south circular roads around the British capital.
London City Hall expected around 110,000 vehicles each day are likely to need to pay the 12.50 pounds (17.22 U.S. dollars) charge for driving within the new zone. Drivers who don't pay face a penalty charge of 160 pounds (220 U.S. dollars), reduced to half if paid within 14 days.
The enlarged zone is an extension of what was the world's first Ultra Low Emission Zone (ULEZ) covering mainly central London.
A City Hall spokesperson said: "The new zone covers one quarter of London and is the largest zone of its kind in Europe. It will bring the health benefits of cleaner air to millions more Londoners. The scheme will operate 24 hours a day, every day of the year except Christmas Day."
The ULEZ is also a crucial step towards London's ambitions to tackle the climate emergency and put the city on the path to be a net zero carbon city by 2030.
Mayor of London Sadiq Khan said: "This is a landmark day for our city. Expanding the Ultra Low Emission Zone today will clean up London's toxic air pollution and help tackle the global climate emergency by reducing emissions."