London's daily congestion charge rises from £8 to £10 from Tuesday.
The zone's western extension was removed by Mayor Boris Johnson on 24 December after a public consultation. He promised in his election manifesto to listen to Londoners' views.
It means drivers will no longer have to pay on streets west of Edgware Road, Park Lane and Vauxhall Bridge Road.
The charge in central London can be cut to £9 a day by registering for a new automated payment service.
This will record the number of days when a vehicle enters the zone and then charge the owner's debit or credit card on a monthly basis.
Anyone who leaves it until the day after travelling to pay the fee will face a £12 charge, compared with £10 in 2010.