The feisty off-spinner from Punjab will become the 10th Indian to play in 100 Tests or more, joining legends such as Sunil Gavaskar, Sachin Tendulkar, Rahul Dravid, Kapil Dev and Anil Kumble.
With 408 wickets from 99 Tests at an average of 32.27 and a strike-rate of 68.1, Harbhajan has been one of India's most prolific bowlers even though he has been enduring a tough phase for some time, playing in only one Test, against England.
In the pre-match press conference, Harbhajan said that he was a "bit nervous" going into the first game.
"It's a big game. (The previous) 99 are gone. Obviously a bit nervous but I am sure I will be fine. I have faced these situations before," the 32-year-old spinner said.