The Croat was handed the reins at the Allianz Arena over the summer as Jupp Heynckes headed through the exits for a fourth time.
He also spent two seasons with Bayern, but is set to cut his continental teeth in a coaching capacity on Wednesday when taking in a trip to Benfica.
Kovac is excited by the challenges which lie ahead, telling Goal in an exclusive interview: “First, I'm looking forward to it, because the Champions League is the highest level. Every single player, every single club and every single coach wants to be there. Now we are there, I am also there.
“The expectation in Munich is always high, this expectation I have towards myself personally and to my players. I was aware of that when I signed with Bayern.
“I also have to say that the group we've been drawn into is very attractive but not easy. Many say Bayern Munich are the favourites and we are the favourites, definitely in theory, but you never know what happens in reality.
“It is interesting. We will go to Lisbon now, where Benfica, like Bayern, are their country’s record champions. Ajax I would also say are record champions. AEK Athens aren’t Greece’s record champions, because that’s Olympiakos.
“These are very interesting opponents and it is very difficult to play against them. That's why we have to be on guard and cannot afford to lose concentration there.
“The first game in the group stage is important, as with any World Cup or European Championship. The first game takes the pressure away or gives the pressure.
“That is why we want to put in a good performance in Lisbon and get a good result in order to make sure there is not as much pressure on the remaining five games."
Kovac has inherited a group of players that have contributed to Bayern securing six successive Bundesliga titles.
As the pedigree of his players without question, only minor tinkering has had to be made in Bavaria.
There have been departures, with Arturo Vidal, Sebastian Rudy and Juan Bernat leaving, but vast experience and a winning mentality has been retained at the core of a hugely successful side.
“I am glad that the core of the squad stayed together,” said Kovac.
“There have been three departures, with Rudy, Vidal and Bernat, but the majority of the team has been playing together for several years, Franck Ribery has been here for 10 years and Arjen Robben has been here for quite some time.
“That's an advantage. The structure stands, the processes stand.
“This, for a coach like I am - many say that I am a young coach, even though I have coached for 10 years now - is beneficial, when you come to such a big club and have pretty good resources, which you can then use.
“The way it is, it is good. We will certainly step by step - as the club always does - try to improve and strengthen, with younger players and of course, bring the necessary quality.
“The quality, as Otto Rehhagel said, is on the pitch and it is 'only about being good or bad and not about being young or old.' I agree with him.”
Bayern will take on Benfica having emerged victorious in their opening five fixtures across all competitions this season, with those successes having landed them the DFL Supercup and a standing back at the top of the Bundesliga table.