The wicket of Khawaja was the 250th Test victim for allrounder Jadeja, who has also scored 2593 runs so far.
Earlier in the day, Australia skipper Pat Cummins won the toss and decided to bat first at the Arun Jaitley Stadium.
The match also marks the 100th Test appearance for Indian batsman Cheteshwar Pujara, who was felicitated by batting legend Sunil Gavaskar before the start of play.
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