The 36-year-old had beaten French qualifier Corentin Loutet 6-3, 6-1 in Rome and was greeting fans after the match.
As he was signing autographs he was whacked on the head by the bottle, which came from the stands.
AP report that it was not thrown, but the metal water bottle fell out of a fan’s rucksack as they leant over the railing to pass Djokovic some paper to sign.
The Serb superstar received medical attention, checked on by doctors after the unexpected clunk on the top of the head, before he was escorted off court.
The world number one’s post-match press conference has been cancelled after the incident.
An update from tournament organisers read: ‘Djokovic was put on appropriate medication and returned to his hotel. His condition is not a cause for concern.’
Djokovic is due to play Alejandro Tabilo in the third round, if he is fit to do so, after the Chilean beat Yannick Hanfmann in his opener.
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