He has been selected in his international position of open-side flanker for the match which will kick off at the Glamorgan Wanderers Memorial Ground in Ely, Cardiff at 7.15pm on Thursday, May 22.
The former Wales Captain who won 23 caps for his country will run out in a WRU Presidents XV team packed with ex Welsh international talent.
Joining him in the back row will be Rob Appleyard at Number 8 with the current Wales squad conditioning coach Mark Bennett completing the breakaway trio.
The front five will feature Anthony Buchanan, Peter Rogers and Martyn Madden with Glyn Llewellyn taking one of the lock positions.
David Bishop and Mark Ring will team up at half back and Mark Douglas will also feature during the game in the scrum half role.
The new Llanelli Scarlets Head Coach Nigel Davies will return to his familiar centre role alongside Roger Bidgood with Nigel Walker and Glenn Webbe on the wings.
Other big names are also likely to be coaxed out of retirement in time for kick off against the Assembly side which will feature a mix of politicians and civil servants.
WRU President Dennis Gethin will donate all proceeds from the match to the WRU Charitable Trust and the National Assembly side, led by Alan Cairns AM, will be raising money for a national cancer charity.
Dennis Gethin said: “I was delighted to accept this challenge from the Welsh Assembly Government especially as it enables us to help the WRU Charitable Trust which does so much good work for injured players.
“Although we champion the elite professional game, rugby will always have a place for these great social occasions.
“It will be a delight to watch so many great ex international players in action again and I know it will ultimately serve to strengthen the great relationship we have with the Welsh Assembly Government.”
The match is in aid of the Bowel Cancer Charity and the WRU Charitable Trust for injured players.
David Pickering said: “I am looking forward to taking part and I’ll be doing my best to cover the yards although I can’t promise I will still be running after eighty minutes.
“It is a long time since I played a game of rugby so I will wait to see how my fitness holds out.
“Some of the guys in the Presidents XV are still extremely fit so I will need to dust of the cobwebs and use all the experience I can muster to keep up.”
WRU Presidents XV: John Williams (WRU staff); Nigel Walker (WALES), Roger Bidgood (WALES), Nigel Davies (WALES), Glenn Webbe (WALES); Mark Ring (WALES), David Bishop (WALES) / Mark Douglas (WALES); Anthony Buchanan (WALES), Peter Rogers (WALES) / James Chapron (WRU Staff), Martyn Madden (WALES), Glyn Llewellyn (WALES), Alex Luff (WRU Staff/Glamorgan Wanderers), Mark Bennett (WALES), David Pickering (WALES), Robert Appleyard (WALES)
Substitutes to appear:
Lewis Tutt (Maesteg Harlequins)
Craig Phillips (WRU Staff)