The centurions dominated the Australian innings before retiring out, as the visitors ended at 327 for five.
The centurions dominated the Australian innings before retiring out, as the visitors ended at 327 for five, with Mitchell Marsh (16) and Matthew Wade (7) unbeaten at the Brabourne Stadium.
Smith and Marsh crafted a 156 run partnership for the third wicket after India chose to field with medium pacer Navdeep Saini bagging openers David Warner (25) and Matt Renshaw (11) with 55 on the scoreboard.
But the new pair played a chance-less innings against an infirm spin and pace attack, with right-handed Smith hitting 12 fours and one six in his 107 run knock before he ended his innings at tea.
His left-handed partner Marsh followed him to the pavilion at tea after hitting 11 fours and a six to reach his 104 in 173 balls as the Kangaroos were 290 for two.
His exit brought Peter Handscomb (45) who played a brisk innings but was caught by Pandhya Priyank Panchal off pacer Hardik Pandya.
Off-spinner Krishnappa Gowtham returned to the pavilion after hurting his hamstring while fielding after lunch followed by Saini, who limped off the field to return shortly before the close.
Australia are touring India for a high profile Test series, with the home side riding on an unbeaten 19-match streak.
The first of the four-match Test series begins on Thursday in Pune.
Australia: 327/5 in 90 overs (S. Smith 107 retired out, S. Marsh 104 retired out; N Saini 2-27, H Pandya 1-64)