"Hodge, one of the top batsmen in last season's inaugural KFC T20 Big Bash League, will lead a selection of explosive Australian cricketers in the two-day tournament," Cricket Australia said in a statement.
Meyrick Buchanan, Cameron Borgas, Travis Birt, Tim Armstrong, Theo Doropoulos and Steve Paulsen have also been named in the squad.
"I'm excited about the tournament, especially because it's been a long time since I've put on the Australian colours," the 37-year-old Hodge said.
"I'll be taking on a bit of a mentoring role as coach and captain and I look forward to sharing my knowledge with the guys, particularly with someone like Meyrick Buchanan (19), who's still only a teenager but has been very impressive so far.
The tournament will take place at the Kowloon Cricket Club from October 27 to 28. The squad was selected by the National Talent Manager Greg Chappell, in consultation with the National Selection Panel.
"We have a good mix of youth and experience in this squad and the younger squad members will benefit from Brad Hodge's presence as captain/coach," Chappell said.
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According to Hong Kong Sixes tournament rules, each team fields six players. Each game consists of a maximum of five six-ball overs bowled by each side, which is increased to eight-ball overs in the final.
Australia won the tournament in 2010, when David Warner and Ryan Carters hit 48 runs from the last over of the final to give the team victory. Following the final, Warner was called up for international Twenty20 selection.
Pakistan currently holds the Hong Kong Sixes trophy.
Australia squad: Brad Hodge (c), Meyrick Buchanan, Cameron Borgas, Travis Birt, Tim Armstrong, Theo Doropoulos, Steve Paulsen.