The No Doubt singer, 47, joins fellow musician Ciara, and actresses Olivia Wilde and Halle Berry, by becoming a spokeswoman for the beauty brand.
In a statement to People.com Gwen said her decision to partner with Revlon was inspired by her passion for cosmetics.
"Ever since I was a young girl, I have used makeup as a form of self-expression," she explained. "I am passionate about makeup and how it can showcase your individuality and creativity. Partnering with an iconic beauty brand such as Revlon felt like a natural fit. I am so excited to continue sharing my love of makeup as a Revlon (spokesperson)."
Gwen, whose signature look combines her platinum blonde hair with bright red lipstick, also spoke to Women's Wear Daily magazine about her new role, revealing she worked behind makeup counters in stores before finding pop stardom.
"I was a makeup artist when I was in my early twenties at the mall; they never trained me," Gwen said. "I worked behind the counter there for Borghese, which nobody bought because it was expensive, and Ultima II, which I think is actually owned by Revlon.
"I'd be like, 'Let me put some makeup on you, let me show you what you could look like. I just remember making people feel so much joy and so inspired and so full of confidence, and that's what makeup can do."
The past two years have seen major changes in the musician's life, after she separated from her husband Gavin Rossdale in 2015 and has subsequently embarked on a relationship with country star Blake Shelton.
Gwen, who met Blake when they were both judges on U.S. TV talent show The Voice, admits her newly-settled love life fitted well with Revlon's current 'Choose Love' marketing campaign.
"It's full of choice and positivity and dreams and truth and I feel like that's aligning exactly with where I'm at in my personal life in the last couple of years and how I've had to kind of choose love, choose truth, choose to be positive and work my way back to a place of using my gift and sharing my love with people," the Hollaback Girl singer added.
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