The England U21 coach will be an interested spectator on Tuesday when the senior side take in their latest 2014 World Cup qualifier.
There will be plenty riding on the midweek encounter, with both sides pushing hard for top spot in Group H and an automatic passage to next summer's finals in Brazil.
Pearce concedes that Roy Hodgson's troops will need to be at their best to prevail on the road, but hopes the momentum they have established in recent fixtures can be maintained.
On the threat posed by Montenegro, Pearce told Sky Sports News HD: "Technically they are a very good side, that's one thing they are.
"We went there with the U21s, in fact for their first game at U21 level and played in the stadium, and it was a tough game for us. Technically they are very good, very passionate about their football. I think it will be a fantastic game.
"We have put ourselves in a really good spirit and good mood with the victory in San Marino and the manner in which we went about our business there, and on the back of a victory over Brazil as well.
"It's an important game, the teams are first and second in the group, so it will be an indicator as to which way the group is going. I think everyone in the set-up will be nice and confident and I'm sure Roy will be pleased with the quality he has got at his disposal."