Both teams entered with 70 points although Ottawa held an edge by virtue of more wins, 30-28.
The win also kept the Senators unbeaten in three meetings with Devils at 2-0-1.
"It was a big game for us," said Shane Hnidy, who also scored for the Senators. "Everybody looks at New Jersey as the Stanley Cup champions and a top team in the league for years now.
"Ottawa really hasn't had playoff success. It's big for us to come in against a team that has had a lot of success. It was a big challenge for the team and tonight we came out and competed hard."
"Not beating them all season doesn't mean anything, not when the playoffs come around," defenseman Scott Stevens said.
Ottawa scored early and late in the opening period to build the 2-0 lead.
Hossa got the second goal with 14 seconds remaining as he knocked home his own rebound.
"Those were key goals," Hossa said. "We scored right away and everybody was pumped up. Then we got the goal on the last shift. It was a big goal for us to go into the dressing room with a two-goal lead."
The teams exchanged goals in the second period as Ottawa took a 3-1 advantage.
Hnidy scored the third straight Ottawa goal at 2:12 with help from a double deflection off two Devils. Hnidy fired a shot from behind the Devils goal that glanced off Alexander Mogilny, and Brodeur's left toe on its way into the net.
The Devils benefitted from an Ottawa deflection on Elias' goal at 8:57. Elias took a wrister from the right circle that deflected past Patrick Lalime.
Sykora got the only goal of the third period, scoring with 20.2 seconds remaining, but the Devils could not get even in the closing seconds.
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