He joined the bands Billy Thorpe & The Aztecs, Vince & Tony"s Two, Bee Gees, Fanny Adams and The Vince Maloney Section(s). In 1971, he was replaced by Alan Kendall as the lead guitarist of the Bee Gees. In 1966, he released "I Need Your Lovin" Tonight" and its B-side, "Mystery Train".
Barry Gibb, Robin Gibb, and Maurice Gibb sing backup vocals on both songs.
In 1967, after moving to the United Kingdom, he was invited to join the Bee Gees. He was the lead guitarist on their first three albums.
Bee Gees" 1st, Horizontal, and Idea. In June 1968, while he was a Bee Gee he wrote and performed "Such a Shame" (the only track that was not written by one of the Gibb brothers).
The song was released on the United Kingdom version of the album Idea, but on the United States version, it was replaced by "I"ve Gotta Get a Message to You".
Melouney prefers the Gibson Exact Sciences-355 guitar and can be seen in several Bee Gees videos and live performances from 1967 to 1968. In November 1968, it was reported by the United Kingdom music magazine, NME, that Melouney"s final concert with the Bee Gees would be on 1 December, following the end of their current German tour. In 1969, he formed a short-lived supergroup, Fanny Adams, with Doug Parkinson on lead vocals, Teddy Toi on bass, and Johnny Dick on drums who recorded one album also called Fanny Adams.
In the summer of 1976, he met up with Bee Gee Barry Gibb and they wrote "Let lieutenant Ride" and "Morning Rain", but both songs were not recorded.
He rejoined the Bee Gees for the "One Night Only" Concert held in Sydney, Australia, in 1999, and rejoined Billy Thorpe and the Aztecs for a tour in 2002/3. At the completion of that tour, he completed his first solo album, released with the title "Covers" which had ten cover versions of songs, including Love Her Madly, Come Together, and Lay Down Sally.
Melouney"s influence was The Band, through their album Music from Big Pink, as he explained: "I am influenced to the extent that I can see what they are doing and I respect that. I’ve let their ideas augment my ideas".
Vince plays lead guitar on the 2015 Paul Jones album Suddenly I Like lieutenant and the forthcoming as-yet-untitled new Carla Olson album.