The former Rovers centre half has signed a one-year rolling contract to return to the club after 22 years.
He said: “It feels really good to be back. Having been here before as a player to be back as the manager is an honour for me.
“I’m looking forward to getting to know everybody around the place.
“The role really appealed to me given the Club Doncaster model currently in place.”
Moore will meet with the players for the first time on Thursday morning and conduct his first media briefing on Friday after training.
Rovers chief executive Gavin Baldwin said: “I’m really pleased to have Darren on board.
“He was a really strong candidate and I am confident he is a really good fit for the club.
“His values match ours, and I’m sure our supporters join the owners and myself in giving him a warm welcome and wishing him well at the club.
“Everyone is now focused on having a good season and building towards the opening game against Gillingham.”
Moore impressed on his introduction to management last year as he almost guided West Brom to Premier League survival, having assumed charge on a caretaker basis following Alan Pardew's sacking with the Baggies on the brink of the drop.
Moore won the manager of the month award for April, having gone undefeated but could not keep them up.
He was handed the job on a permanent basis and mounted a promotion push but was sacked in March for failing to “engineer consistency of form and results” according to club officials. West Brom sat fourth in the Championship at the time.
Moore made more than 80 appearances for Rovers after being signed from Torquay in August 1995 before being sold to Bradford City two years later.