The former Liberty X star was one of 24 acts who went head to head in a vocal battle, with the losing act facing the possibility of going home.
Kevin Simm battled it out against Faith Nelson
Staged in a setting resembling a boxing ring, the 35-year-old was up against teenager Faith Nelson.
The pair duked it out for the all-star panel of will.i.am, Boy George, Paloma Faith and Ricky Wilson to the song Spotlight by Oscar-winner Jennifer Hudson.
However, their team coach Faith felt the 17-year-old had performed better on the night and Nelson automatically progressed to the next stage.
Chorley-born Simm had struggled with his vocals in rehearsal due to illness, but he was given a second chance in the competition.
Once a coach has selected their battles rounds victor, the losing singer becomes available to a rival panellist for a "steal".
To do so, they must hit their buzzer for that act before the clock runs down.
Kaiser Chiefs frontman Wilson, who had one steal left, buzzed for Simm.
Paloma Faith dumped Kevin from her team
As a result, the Lancashire singer is now on the Yorkshireman's team, and he still has an opportunity to win this year's series.
Talking about the result, Simm said: "I felt like I could really end up with egg on my face."
Wilson explained why he decided to steal.
"I really felt Kevin deserves this shot," he said. "I've never taken a steal through to the finals before, but he has got a shot."
Along with Michelle Heaton, Tony Lundon, Jessica Taylor and Kelli Young, Simm failed to make it into Popstars' winning group Hear'Say, whose members included Myleene Klass and a pre-Coronation Street Kym Marsh.
They instead went on the form Liberty X and won the Brit Award for best British single in 2003 with their chart-topper, Just A Little.
Liberty X enjoyed several more hits before calling it a day in 2007, but the band out-lasted Hear'Say, who had split in 2002.
Simm released his album Brand New in 2008, but he experienced commercial failure as a soloist.
A dramatic night of cheers and tears saw will.i.am use his remaining steal for Bath-born singer Eli Cripps, who is half Nigerian and half Welsh.
Paired with Welshman Leighton Jones, the pair battled to If I Were Your Woman by Gladys Knight and The Pips.
Their coach Boy George selected Jones as the victor, but viewers will see Cripps on the American's team in the knockout stage next week.
"I held out for Eli Cripps and went through a lot of pressure and I'm happy that George left her available for a steal," will.i.am said.
The battles rounds winners hoping to make it to the live shows are: Vangelis and Chase Morton from team Boy George and will.i.am's Lauren Lapsley-Browne, Lyrikal and Harry Styles lookalike, Tom Rickels.
From team Wilson, the winning contestants are Kagan, Mia Sylvester and teenager Rachel Ann, who sang barefoot.
They will be joined by team Faith's Beth Morris and Deano.
'The Voice' continues next week.