The band was formed in late 1966 with the amalgamation of Perth groups The Spektors and The Winstons. They capitalised on the success of both the former bands, plus the interest created by having two lead singers in Scott and Lovegrove. Inspired by The Rolling Stones, The Beatles, and local stars The Easybeats, they enjoyed considerable local success and released a few singles.

In late 1967, The Valentines moved to Melbourne in search of greater success, and soon toured other major cities. With a development towards the popular Bubblegum sound late in 1968, the band became more in demand, particularly among teenage girls. However as the fashion for bubblegum music wore off, The Valentines struggled to retain their musical credibility despite a turn towards rock music. With differing opinions within the band concerning musical direction, and a much-publicised drugs bust in September 1969, group stability began to suffer. Although they still had a strong fanbase in certain areas of the country, especially back home in Perth, The Valentines decided to disband amicably in August 1970.

Scott had built a strong reputation as a powerful vocalist and soon joined Fraternity, and later AC/DC. Lovegrove found success as a music journalist, and guitarist, Wyn Milson became a sound engineer.

Warwick Findlay, drums 1966 - July 1968
Bruce Abbott, drums early 1968
Doug Lavery, drums July 1968 - 1969
Paddy Beach, drums May 1969 - Aug 1970
John Lockery, bass guitar 1966 - 1968
John Cooksey, bass 1968
Vince Lovegrove, vocals 1966 - 1970
Wyn Milsom, lead guitar 1966 - 1970
Bon Scott, vocals 1966 - 1970
Ted Ward (Ted Junko), guitar 1966–1969 and bass guitar 1969–1970