Reports of discontent in the PSG dressing room have emerged after Neymar, a world-record €222 million signing from Barcelona in August, argued with established centre-forward Cavani over who should take a spot-kick in the 2-0 victory at home to Lyon in Ligue 1.
The Uruguayan won that battle of wills but failed to score and Emery has since assured he has spoken to both players regarding the issue.
Neymar sat out a 0-0 league draw at Montpellier last weekend but is due to return to the starting XI when Bayern go to Parc des Princes on Wednesday.
Should the visitors commit a foul inside the area, all eyes will be on PSG's expensively assembled strikeforce — old and new — to try to glean the outcome of Emery's decision.
"Many players are able to do this," the coach said of taking responsibility from 12 yards out.
"Many want it. Cavani and Neymar are ready. There will be a lot of penalties and they will both get them.
"I spoke with the two. I told them how things should happen."
Emery acknowledged Bayern are among the perennial favourites to capture the continent's elite club competition but also knows PSG are now deemed to be within that bracket.
"It's a big team, with a great history," he said.
"They are among the candidates to win the Champions League."
Asked about PSG's transition to that status, the former Sevilla boss said: "I was on the other side. I watched the great European teams, with the best players in the world.
"We have taken an important step to be part of these teams.
"We have more sporting enemies. The other teams see that we are serious. There is a real competition between PSG and the big teams.
"It's good for us."
Emery also offered an endorsement of Julian Draxler, who shone after arriving from Wolfsburg in January but has found it tougher to earn a place in the first XI following the arrivals of Neymar and Kylian Mbappe from Monaco.
"He is an important player," he said of the Germany international playmaker.
"He had six good months last season. He began late on his return from the Confederations Cup. He offers versatility. He can help us by starting or by coming on."