The 68-year-old 'Shout' hitmaker is a member of an exclusive club of artists, which includes Sam Smith, Adele, Dame Shirley Bassey, Sir Tom Jones, Duran Duran, Sir Paul McCartney and more, who have been picked to record the title track for a 007 movie.
To celebrate the third edition of Vauxhall's 'Great British Legends' series, Lulu drove a Vauxhall Astra around the suburbs of her hometown of Glasgow in Scotland.
During the drive she was asked about the song 'The Man with the Golden Gun' - written by Don Black and John Barry - that she recorded for the 1974 film of the same name starring Sir Roger Moore as Bond and the late Sir Christopher Lee as main villain Francisco Scaramanga.
She admitted it was a good experience but declared: ''I think that mine was probably the worst one ever! Mine was not a great song.''
When asked if she had heard Madonna's 2002 Bond tune 'Die Another Day', she joked: ''Oh yes, hers was pretty bad. Probably Madonna and I - that's probably the only time Madonna and I could be together on anything.''
Lulu also recalled how her involvement in the spy franchise came about.
She said: ''They asked me, I don't say, 'How did you ask me? Why did you ask me? I just thought, 'Oh that's dead cool.' Shall I tell you why it was cool, because John Barry wrote the music but I always had a little crush on John Barry so I was thrilled to be working with him.''
In the interview Lulu also revealed how she ended up re-recording David Bowie's 1969 track 'The Man Who Sold the World'.
Speaking about her hit 1976 collaboration with the late rock legend, she explained: ''It was Bowie's idea to do that song. I think I first met him in a studio with Iggy Pop and Iggy Pop gave me a filthy look - he just did not want me around. But the meeting sticks out in my mind.''
Lulu explained that he came to see her in Sheffield where she was on tour and invited her to a concert. But it was at the after-party where he declared his love of her voice.
She recalled: ''During the night he said to me, I think very early on he said, 'I love your voice,' and I was like, 'Oh my God!' and he said, 'I wanna make a mother f**king hit with you' and I thought, 'Yeah right, we'll see.' I was very impressed. I was very flattered. That's how it happened.''
The following day Bowie called to invite her to his Hyde Park hotel where he played his version of 'The Man Who Sold the World'.
Vauxhall's 'Great British Legends' series is available as four episodes online at www.vauxhall.co.uk/greatbritishlegends.
You can also visit Luluofficial.com for details about Lulu's upcoming tour.