Currently playing for Hull KR in the Super League, the 33-year-old will hang up his boots after leading PNG at the World Cup later this year.
Martin will reunite with his Hull KR coach Willie Peters, set to take on the same role at the Chiefs who will enter the NRL in 2028.
The Australian-born second-rower, whose father Steve is from PNG, is one of the country's most respected rugby league figures.
He captained the Kumuls for nearly four years and is the all-time leading scorer in 18 Test appearances.
Making his NRL debut with Canterbury in 2018, Martin played more than 160 Super League matches with Leeds Rhinos and Hull KR.
Martin also holds the world record for the most consecutive goals kicked, with 41 straight conversions during his time at Leeds.
As football operations manager, Martin will oversee player welfare and integration programs, while also helping support players and families transitioning to PNG ahead of the club's inaugural NRL season.
PNG Chiefs General Manager Football Michael Chammas said the appointment of Martin was part of the club's plan to "build a football program grounded in Papua New Guinean identity".
"Anyone who has ever met Rhyse will talk about the quality of person he is and how passionate he is about Papua New Guinea," Chammas said in a statement.
"The combination of those two things makes him such an important off-field signing for the club and we are proud to have him joining our football staff.
"Rhyse has had an incredible career as a player but he still has so much to offer the sport."
The Chiefs recently announced they had signed former Parramatta winger Luke Burt as an assistant coach.
The 44-year-old is the first member of Peters' coaching staff to be unveiled and will commence his role in November 2027.
Four-time premiership winner Jarome Luai will join the club from West Tigers while South's try-scoring winger and PNG international Alex Johnston has also committed to the Chiefs.
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