From 29 August, drivers of the most polluting cars will have to pay £12.50 to enter any London borough, Mayor Sadiq Khan announced last week.
A public consultation found 80% of people in the affected areas were opposed the expansion of the zone.
Now Hillingdon, Harrow, Bexley and Croydon councils have announced their opposition to the widening of the zone.
The four Conservative-run councils’ leaders cited poor transport links in the outer boroughs and a stronger dependency on cars to get around as their major issue.
They say the lowest-income communities will be the most affected and are calling for greater investment in outer borough transport before the ULEZ expansion, known as ULEX.
London’s Labour Mayor Mr Khan said the cost of living had been a “key consideration” for him, adding that plans were in place to relieve the effect on drivers when introducing the new plans.
He said that expanding the ULEZ London-wide had “not been an easy decision” but that “in the end, public health comes before political expediency”.
There will be an increased scrappage scheme fund of £110m and those who scrap more polluting cars will also be offered travelcards. Under the plans, disabled drivers will be entitled to a grace period until 2027.
City Hall also said bus networks would be improved in outer London.