Referred to as 'Super Thursday', the polling also covers votes for new mayors in Bristol, Liverpool and Salford as well as parliamentary by-elections in Ogmore and Sheffield Brightside.
Polls are also taking place for the Scottish Parliament, National Assembly of Wales, the Northern Ireland Assembly and for 124 councils in England.
However, not everything went smoothly after a number of voters were turned away from booths in Barnet, north London, due to errors on the electoral lists.
Earlier, Prime Minister David Cameron arrived with his wife, Samantha, at a Westminster polling station to cast his vote, presumably in favour of his Conservative Party's London mayoral candidate Zac Goldsmith.
Labour's mayoral candidate SadiqKhan voted at his local polling station in Streatham, south London, while Goldsmith voted in Barnes, southwest London.
Khan, 45, the son of a Pakistani immigrant bus driver, is believed to be leading the race to take over from Boris Johnson as London mayor and has held on to a strong lead throughout the mayoral campaign.
Experts say that the race is not yet decided as a low turnout could change things at the last moment.
Polling across the UK will close at 10 pm today and results will begin pouring in gradually from about 11 pm with final results not expected before tomorrow afternoon.
The mayor of Londonis elected under a "supplementary vote" system where voters indicate theirfirst and secondpreference candidates.
If no candidate receives over half of the first-preference votes, the top two candidatesproceed to asecond round, where the other candidates are eliminated and second-preference votes are distributed between the two remaining contenders.
