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Pickering, who is currently a senior consultant at Watson Wyatt, will take up his new position at the independent trustee company from January.
In addition to his role as chairman, he also hopes to take on a number of trusteeships on behalf of BESTrustees.
Pickering said: "Leaving a good job, even for your own volition, is always somewhat daunting. however, it's time for a fresh challenge."
He added: "I have been advising trustees for most of may career so it's exciting that I'm about to become one. It must be every coach's dream to leave the touchline and join the team, so for me, this is a dream come true."
Managing director of BESTrustees Chris Gilchrist said: "I am delighted that Alan is joining us as chairman. His wisdom and down-to-earth style will be an asset at our board meetings, and our clients will benefit from his decades of pension experience."
Pickering has a wide range of experience in the market, including having chaired the National Association of Pension Funds between May 1999 and May 2001, and been a member of the board of the Pensions Regulator.
He has spent 16 years with Watson Wyatt, having joined in 1992. He previously spent 20 years with the EETPU.
Pickering added: "Watson Wyatt has given me opportunities that were beyond my wildest dreams. I shall forever cherish fond memories of colleagues and clients alike."
Outgoing chairman Woodward founded BESTrustees with Gilchrist in early 1992 and has since guided the company's growth from two to 24 professionals.
Location: Eastbourne
Salary: Salary to £35,000 plus ongoing bonuses
Location: London
Salary: £28000 - £32000 per annum