The station is on Isambard Kingdom Brunel's former Great Western Main Line running out of London Paddington to the Thames Valley, Bristol, South Wales and the West Country.

The line was opened on 4 June 1838, initially running to a temporary Maidenhead station to allow completion of the famous brick arch bridge over the River Thames just west of the station. The station at Hayes opened in 1868.

From 1 March 1883, the station (then named Hayes) was served by District Railway services running between Mansion House and Windsor. The service was discontinued as uneconomic after 30 September 1885.

Hayes is the location of the junction for the Heathrow Airport branch and is a station on Crossrail.

The film 'Trains at Hayes Station' showing trains passing through the station with stereophonic sound was filmed from the roof of the defunct Aeolian pianola factory just north of the station. The factory had been purchased by HMV when the pianola company had collapsed owing to fraud and technological obsolescence. The film is almost the first demonstration of stereophonic sound to accompany moving pictures, an invention of Alan Blumlein.