With center Evgeni Malkin recovering from a lower-body injury, Penguins coach Mike Sullivan moved Hornqvist to first-line right wing with center Sidney Crosby.
WATCH: All Penguins vs. Predators highlights
"I think we play really well together," Hornqvist said of Crosby, who assisted on his first goal. "We know exactly where we are on the ice and I think we showed that tonight. We got some really good looks on the first shift. Almost had a tap-in on the back door. Just missed it a little bit. I think the other lines played really well too. It was a big team effort for us."
Pittsburgh (31-13-5) avoided a third straight loss.
"It was a little bit of a mixed bag," Sullivan said. "Halfway through the game, I think we gave up 12 shots. So I think that aspect of the game we really liked. … The chances we gave up, they seemed to come in flurries. But a lot of the game, we certainly made a step in the right direction."
Nashville (24-18-8) failed to extend its point streak to six games.
"We're going to have to learn from this," Predators defenseman Ryan Ellis said. "We had a streak going. We were playing really good hockey and we need to regroup, refocus and come back from this game better."
Penguins goalie Matt Murray made 37 saves to respond from losing two straight in regulation for the first time in his NHL career. He is 10-1-1 at home this season.
Calle Jarnkrok gave Nashville a 1-0 lead with 5:56 remaining in the first period before Pittsburgh scored four straight. The flurry began on Kunitz's sixth goal of the season with 3:41 left in the first.
Daley gave Pittsburgh a 2-1 lead 3:10 into the second period. The goal, which came on a slap shot shortly after a failed power play, was Daley's fifth of the season, second in five games.
Hornqvist extended it to 3-1 when he snuck a wraparound between Pekka Rinne's right skate and the left post with 8:53 remaining in the second.
Hornqvist scored again when Nick Bonino shot off Austin Watson to him in front of the crease, where he held off Matt Irwin and shot off Rinne's glove. Hornqvist's 14th goal made it 4-1 with 3:48 left in the second.
Colin Wilson made it 4-2 with a power-play goal at 3:18 of the third period.