Forty bus stops across south London are to be illuminated using solar power as part of a trial by transport chiefs.
The mayor says solar power is a cheaper and greener solution
Energy from the sun will be captured by a specially-fitted canopy and stored in batteries during the day, to light up the bus stop sign and timetable after dark.
London's bus stops are currently powered from the mains supply, but the expense and the difficulties of connecting in some areas have made Transport for London (TfL) look for another solution.
The first bus stop to be lit up by the sun's energy will be unveiled in Eaton Square, south west London, on Monday.
Ken Livingstone pledged to put the environment at the heart of London government in his campaign to become mayor in 2000.
He also wants to encourage more Londoners to use the bus network, which has been expanded with the introduction of the congestion charge.
Bus use has risen by 6% over the past year and trips on the night bus have grown by 20%, according to TfL.
They say lighting up the bus stops also makes people feel safer when using the service at night.
Mr Livingstone said: "Using solar power is a simple environmentally-friendly solution to a frequent complaint about the difficulty of reading timetables and feeling secure at night."