The 38-year-old, a veteran of 165 Test matches, will bow out after an 18-year career at the top level, during which time he has established himself as arguably the greatest all-rounder in the game - scoring 13,174 runs and taking 292 wickets as well as 199 catches prior to the India clash.
He remains available for selection for limited-overs cricket and has set his sights on playing for South Africa at the 2015 World Cup, but he will begin his final Test appearance on Thursday at Sahara Stadium in Durban.
In a statement released by Cricket South Africa, Kallis said: "It’s been an honour and a privilege to have been part of the South African Test team since making my debut 18 years ago. I have enjoyed every moment out in the middle but I just feel that the time is right to hang up my Test whites.
"It wasn’t an easy decision to come to, especially with Australia around the corner and the success this team is enjoying, but I feel that I have made my contribution in this format.
"The last two years specifically have been a memorable journey with an exceptional group of cricketers.
"I am fortunate enough to have ended my Test career amongst a group of talented cricketers but more importantly, friends whom I will cherish for years to come.
"I don't see it as goodbye because I still have a lot of hunger to push South Africa to that World Cup in 2015 if I am fit and performing."
Proteas coach Russell Domingo admitted that Kallis will be hard to replace.
He said: "The impact Jacques has made on South African cricket has been immense, not just as a player but as a human being. I'm not sure we will ever see another player of that stature very soon.
"Jacques' calmness, maturity and presence in the change room will sorely be missed and hopefully he will still be able to play a role in this team's success in the near future.
"He has ambitions of playing in the 2015 World Cup and it will be important for us to manage him accordingly so that he is in prime form leading into the tournament."
Cricket South Africa president Chris Nenzani also paid tribute to Kallis, insisting that he will bow out with a place among the greats of the game well and truly secured.
"We are truly entering a new era with three of the icons of the game – Ricky Ponting, Sachin Tendulkar and now our own Jacques Kallis – departing the Test arena within a short space of time," he said.
"It is a time for reflection not only on Jacques' enormous contribution to the game of cricket but also the legacy he leaves behind him.
"South Africans love their sporting heroes and Jacques is right up among the best; not only that but he has been there for the best part of two decades.
"At a time when we live in a fast-changing world and not always for the better he has remained true to the best traditions of the game and of sportsmanship and has always risen above any kind of controversy.
"Jacques, we thank you not just for what you have meant to South African cricket and indeed to the world of cricket but more particularly for the example you have set in being a model South African for our youth and future leaders."