Friday night's Stradey Park quarter-final showdown pitches Llanelli, one of only two teams to claim a 100% Heineken Cup pool stage record this season, against a side unbeaten away in Europe for almost 18 months.
And Scarlets scrum-half Peel knows Llanelli's quest for their third Heineken Cup semi-final appearance represents a hazardous mission.
He said: "We've put ourselves in a great position to push on, although we realise Munster is a huge challenge.
"The pool stage seems a fair way off now, but the players have been working very hard since we qualified. There is still a great hunger in the bellies of the players.
"Come European time, we seem to click, and we all know that things will need to go well for us if we are to beat Munster. We will have to bring our best game of the season to Stradey on Friday night.
"After playing teams like Ulster, Toulouse and London Irish away and getting maximum points in our pool, we know what we are capable of, but this is going to be a massively intense game."
Munster's ninth successive quarter-final appearance - they have won six of the previous eight - was secured despite losing their long unbeaten record at Thomond Park when Leicester triumphed in Limerick two months ago.
But Llanelli are viewed by many as dark horses to lift the trophy this term and become Wales' first European champions in the 12th season of Heineken Cup rugby.
Peel added: "We have had some disappointments in Europe in recent years, but those defeats will only spur us on to better things.
"It is a big ask for us to reach a first Heineken Cup final, but it is something we are definitely up for.
"It would be a fantastic honour to to reach a Heineken Cup final with the Scarlets. To reach the final and win the title would be a dream come true, and right up there with anything I have achieved.
"We have had a good campaign so far and played some really good rugby along the way, and it would be a shame to let all that good work slip away now."
Llanelli and Munster have never previously met in top-flight European competition, but Scarlets' Magners/Celtic League record against them at Stradey Park is impressive, having reeled off four successive home wins.
And Llanelli have received a major boost ahead of the sold-out clash with fly-half Stephen Jones being named in the starting line-up.
Scarlets boss Phil Davies has announced Jones at number 10, even though he had been a major doubt after suffering a wrist injury that ruled him out of Wales' RBS 6 Nations finale against England earlier this month.
Davies said: "I have got no problems whatsoever in naming Stephen in the squad.
"He is fine, good to go. He is a very influential player, a world-class player, and he is very important to us as a team.
"He's a great member of the squad. It is great to have him involved, and I am looking forward to getting a good performance from him."
Scarlets' Wales wing Mark Jones, meanwhile, faces a fitness test after suffering a blow to his knee in training. If Jones is ruled out, then Matthew Watkins will replace him, with Morgan Stoddart joining the replacements.
Munster, already without injured lock Paul O'Connell and full-back Shaun Payne, have concerns surrounding John Kelly, Anthony Horgan, Mick O'Driscoll and Anthony Foley.
Ronan O'Gara will captain the side in O'Connell's absence, while former All Blacks ace Christian Cullen is likely to wear the number 15 shirt instead of Payne.