Catt, who was instrumental in the Exiles' charge to the Guinness Premiership Final earlier this season, was born in Port Elizabeth and brought up in South Africa before moving to England in 1992.
He represented Eastern Province, one of the sides who will make up the newly-formed Southern Kings Franchise, early in his career and now looks to set to return to his roots for what could be his final game of top-class rugby.
Catt toured with the Lions in 1997 and 2001, joining the first of those tours as a replacement and playing in the third and final Test against his countrymen in Johannesburg.
The 37-year-old has yet to confirm whether he will continue playing next season and an unexpected chance to face the Lions could provide the perfect end to a superb career for the World Cup winner.
If he does play against Ian McGeechan's men in just under a fortnight's time, Catt will follow Tom Reid and Riki Flutey in playing for and against Britain and Ireland's elite.
Reid achieved the feat when he faced the Lions for Canada in 1966 having been a Lion himself in South Africa seven years later.
New Zealand-born Flutey followed suit less than a week ago when he appeared as a replacement against the Royal XV during the first game of the current tour after previously playing against the 2005 Lions for Wellington.
The Southern Kings, who hope to be admitted to an extended Super 15, are coached by former Northampton Saints and Ulster boss Alan Solomons.
Solomons has submitted a list of names he would like to see face the Lions in the final match before the first Test against the Springboks but that list needs to be signed off by Southern Kings chief selector and president of the Boland Rugby Union Francois Davids. Player availability would also need to be confirmed but Catt could soon be writing his name in the history books.
Solomons' proposed matchday 22 also features Harlequins duo De Wet Barry and Gary Botha, Saracens scrum-half Neil de Kock and former full back Brent Russell, Ulster pair Robbie Diack and BJ Botha, ex-Bath and Northampton wing Wylie Human and Catt's London Irish team-mate Faan Rautenbach.
Provisional Southern Kings team list
Tiger Mangweni, Vuyo Zangqa, Rudi Coetzee, De Wet Barry, Wylie Human, Mike Catt, Neil de Kock, Daan Human, Hanyani Shimanga, BJ Botha, Mpho Mboyosi, Ross Skeate, Trevor Hall, Solly Tyibilika, Darren Nel
Replacements: Gary Botha, Faan Rautenbach, Lungile Payi, Robbie Diack, Josh Fowles, Mzwandile Stick, Brent Russell