Djokovic, 37, chasing a record 25th Grand Slam title, won 6-4, 6-1, 6-2 and goes on to face either Gael Monfils of France or Italian 30th seed Lorenzo Musetti.
Djokovic holds a 19-0 winning record against Monfils and has defeated Musetti four times in five meetings.
However, the Italian gave the Serb a major scare at the French Open in 2021 when he won the first two sets before having to retire injured in the decider.
Top seed Djokovic dropped his opening service game against 63rd-ranked Carballes Baena but from 4-4 in the first set he reeled off 14 of the last 17 games to storm to victory on the back of an impressive 43 winners.
"It was a difficult match against Roberto. He hit a lot of very good and precise shots," said Djokovic.
"The last game of the first set I played really well and started to play at a higher level. At the end of the match I was then playing very well."