It was announced on Wednesday that the mayor would host a weekly podcast, entitled Clear The Air, on LBC.
But mayoral aides said there were no plans for an episode on the Silvertown tunnel, arguably the most controversial proposal during Mr Khan’s time in office due to concerns it will worsen air quality.
A spokesperson for the Stop the Silvertown Tunnel Coalition said: “Any guests appearing on this new podcast should know they’re participating in a cynical PR offensive designed to greenwash dirty, climate-wrecking, policy.”
Sian Berry, leader of the Green party on the London Assembly, said: “Perhaps the mayor could invite the leaders of local councils, campaigners and others onto his podcast and hear from them why building a new urban motorway is unacceptable.”
Tunnelling work on the £2bn tunnel under the Thames began earlier this month. It will link Newham to the Greenwich peninsula via a 1.4km road tunnel and is due to open by 2025.
The London fire brigade had to be called to the site late on Tuesday night when a conveyor belt drive unit caught fire. About 25 people had already been evacuated before crews arrived.
Mr Khan believes the new tunnel is needed to tackle congestion at the Blackwall tunnel, where peak-hour queues can often stretch miles, especially for northbound traffic.
It will be inside the ultra-low emission zone - meaning any vehicles that fail to meet the exhaust emission rules will have to pay a daily charge. The tunnel will have a priority bus lane.
Announcing the podcast, LBC said Mr Khan would speak to “public leaders, politicians, environmental activists and celebrities from around the world who are helping lead the fight against climate change”.
The first episode, with former Labour party leader Ed Miliband, will be released on Tuesday next week.
Other guests include Notting Hill film director Richard Curtis, model Lily Cole and wildlife TV presenter Steve Backshall.
Mr Khan will also speak to Rosamund Adoo-Kissi-Debrah, whose daughter Ella died following a fatal asthma attack caused by toxic air pollution from the South Circular Road, the Mayor of Los Angeles Eric Garcetti, Margaret Thatcher’s environment secretary John Selwyn Gummer, now Lord Deben, and the Mayor of Freetown in Sierra Leone, Yvonne Aki-Sawyerr.
Mr Khan said: “This summer we’ve seen deadly heatwaves, destructive wildfires, and dangerous flooding across the UK and the world.
“At times, the threat posed by climate change can seem overwhelming, but there are inspiring people across the globe – of all ages and backgrounds – determined to help tackle this crisis head on.
“Clear the Air invites us to take a breath and reflect on the challenges facing our planet, the scale of the action needed to meet them and the steps we can all take to help secure a safer, fairer and greener future for all.”
A mayoral aide said Mr Khan’s own policies were likely to be mentioned but the podcast would focus primarily on the guests and their experience of seeking to tackle climate change.
The anti-Silvertown campaigners are holding a public meeting on Sunday October 9 to discuss how the tunnel will affect residents.
Victoria Rance, a spokeswoman for the Stop the Silvertown Tunnel Coalition, said: “Sadiq Khan talks about air quality and his achievements while ignoring the fact that over 16,000 children attend schools by Silvertown Tunnel approach roads in Greenwich and a similar number in Newham.
“Already these schools are overwhelmed by HGVs building the tunnel, and when it’s opened the HGV lanes will bring thousands more vehicles directly past them. Parents have started moving children out of these schools.
“Sadiq Khan refuses to discuss our concerns about children’s health and the damage his toxic project will cause both short and long term to the health of residents, and especially our children here.”
LBC has been approached for comment.