Musetti, Rune set winning pace for ATP seeds in Toronto
The pair began after byes and wasted little time in advancing into the third round, with Musetti hammering Australian qualifier James Duckworth 7-5, 6-1 while Rune dispatched big hitter Giovanni Mpetshi Perricard 7-6 (9/7), 6-3.
Top seed Alexander Zverev was making his start later, with the German world number three facing Australian Adam Walton.
The event is missing the absolute cream of the player field, with both number one Jannik Sinner and second-ranked Carlos Alcaraz out with injury and fatigue issues.
Musetti, a former semi-finalist at both Wimbledon and Roland Garros, was ruthless with Duckworth, advancing in 82 minutes. He broke for a set and 5-1 on his opponent's double-fault and finished up a game later with an ace.
The Italian is coming back into form after losing his only grass match of the summer (Wimbledon) and then going down last week in his Washington opening match.
His last victory came in early June in the Roland Garros quarters.
Musetti had 17 winners while Duckworth was undone by more than 30 unforced errors.
The Italian next faces American Alex Michelsen, a 7-6 (9/7), 6-3 winner over Chilean qualifier Tomas Barrios Vera.
Rune, who was back in action a month after a first-round Wimbledon defeat, handed French Mpetshi Perricard a fourth career loss against top 10 players.
Denmark's four-time finalist at the Masters level produced his first hardcourt win since last March at Indian Wells.
"I tried to stay calm and focus on my serve," Rune said after his 75-minute victory. "There's sometimes not a lot you can do against his big serve, but I was trying as much as possible.
"I had a good start to the second set. I'm very happy with the match in general. I've not served like this for a while. We've been working on small adjustments.
"My serving felt good and I trusted it all the way."
World number nine Rune limited his unforced errors to just 10 -- less than half of those struck by his opponent.
Elsewhere, 11th seed Karen Khachanov beat Juan Pablo Ficovich of Argentina 6-4, 6-2.
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