Bayo Dosunmu, 46, of Hammersmith was arrested on Sunday, June 23 in the Westminster area.
The top executive of Lambeth Council resigned following allegations of drug and alcohol use while driving.
It is alleged that Bayo Dosunmu left the scene of an automobile accident in Westminster at the end of June.
The 46-year-old Hammersmith resident was detained on suspicion of failing to stop, operating a car while intoxicated, possessing class A narcotics, and operating a vehicle without insurance.
Following the arrest, Lambeth council said Mr Dosunmu would be taking some time “away from work”.
On Wednesday a town hall spokesman confirmed he will officially leave the £185,000-a-year post from next week.
“Bayo Dosunmu has stepped down as chief executive of Lambeth council with effect from Monday July 15, 2024,” a spokesman said.
“Fiona Connolly is currently acting chief executive and the council will shortly begin the process to recruit a permanent chief executive.”
A Met Police spokesman said: “Bayo Dosunmu, 46, of Hammersmith was arrested on Sunday, June 23 in the Westminster area.
“He was charged on Monday, June 24. He will appear at Westminster Magistrates’ Court on Thursday, August 1.”
Dosunmu received a salary of around £185,000 a year as boss of the Labour-run local authority, plus extra payments for acting as the borough’s returning officer during elections.
He was appointed Lambeth’s chief executive in 2022 having previously acted as the borough’s deputy chief and strategic director for resident services.
Before that, he was an executive director at Homes England and assistant chief executive at the Homes and Communities Agency.
He also served at a senior level in a range of civil service roles including for the Welsh Government and the Olympic Delivery Authority.