The ex-defender has succeeded Matt Potter at the North West Counties League Premier Division side.
The 44-year-old has taken his first job in management in the process and says he has been inspired by Pep Guardiola and Jose Mourinho.
"This is a very proud day for me," said Chimbonda, 44.
"It is a great honour to become manager of a club with a history as rich as that of Skelmersdale United Football Club.
"I've been inspired by Guardiola, Mourinho, Simeone and Zidane, and as such just like those great managers, my philosophy will be to play attractive football."
READ MORE ON TALKSPORT
Charlton to face eighth-tier non-league side as FA Cup first round draw made
Sir Jim Ratcliffe: Britain's richest man is a boyhood Man United fan set for takeover
Chimbonda is best remembered for his spells in the Premier League with Tottenham and Wigan, playing for Spurs across two spells.
But he also played for several other top clubs including Sunderland., Blackburn and QPR.
As his career approached its end, Chimbonda's love of football did not diminish as he happily went down the tiers to continue playing.
Some of the non-league clubs he played for include Market Drayton Town, Washington and Ascot Town.
Most read in Football
Charlton to face eighth-tier non-league side as FA Cup first round draw made
Philippe Clement wins race to be new Rangers manager ahead of Kevin Muscat
Henderson makes first social media post after being booed at Wembley by England fans
Gillingham interim boss sent off for tripping over Walsall player in heavy defeat
Chimbonda will take charge of his first game on Wednesday when Skelmersdale United take on Kendal Town in the Macron Cup.
The Lancashire outfit finished 11th in the Northern Premier League Division One West last season, the eighth tier of English football.
However, they were relegated as their ground did not meet Football Association ground grading regulations.
Chimbonda arrives at a club in crisis, though, who have taken just three points from 16 games this season.
It has left 10 points adrift of safety and will need a miracle already to stay in the division, sitting at the bottom of the table.
"We are extremely pleased to announce that Pascal has agreed to join one of the most prestigious clubs in non-league football," said Skelmersdale United chairman Frank Hughes.
"We've set out to create a philosophy that will continue throughout the ages. We are going to be the standard bearers for great football, because that is what our supporters demand, and is exactly what they deserve.
"This is a major coup for the club, and we are very excited about the future."