Kean left Rovers in September last year, stating he had been forced to resign, with the club in third place in the Football League Championship.
A former first team coach, he was installed as caretaker manager with Rovers following Sam Allardyce's sacking in December 2010 and was given the role permanently a month later, but was unable to prevent the Lancashire club from being relegated the following season.
Kean stayed on despite heavy pressure and criticism from fans, before leaving his post at the start of the 2012/2013 season.
The Glasgow native had previously expressed interest in coaching in Asia in an interview with Sky Sports in July.
"I'm open-minded enough to consider all areas of the world whether it's Asia, the UK or Europe," he told skysports.com.
"I have been in Europe and the UK but I've never coached or managed in Asia, although it's something I would certainly consider. I have no preference really. I'm just to open any good offers."Kean will be replacing Croatian Vejran Simunic who annouced his departure from the 2013 S.League League Cup runners-up earlier this month.
Simunic led DPMM to a second-place finish in the 2012 S.League season and won the League Cup as well but failed to replicate the success this year, with DPMM slated to finish in the bottom-half of the S.League.
DPMM have also confirmed that Brazilian midfielder Rodrigo Tosi will be retained, with the club in the hunt for a big-name marquee signing.
The Bruneian club will also be involved in a Participation Agreement Renewal Signing Ceremony with the Football Association of Singapore (FAS) on Tuesday morning at the Jalan Besar Stadium. The ceremony will be graced by FAS President Mr Zainudin Nordin, Mr Lim Chin, CEO, S.League, Deputy Chairman of DPMM FC, YAM Pengiran Maharaja Setia Laila Diraja Sahibul Irshad Pengiran Anak Haji Abdul Rahim bin Pengiran Indera Mahkota Pengiran Anak (Dr) Kemaludin Al-Haj, and Mr Mohd Ali Haji Momin, Team Manager, DPMM FC.
The S.League is currently four rounds away from concluding the 2013 season. Tampines Rovers have a 12-point lead and are on course to retain their title. The 2014 S.League season is expected to begin in mid-February.