The Harlequins star, who featured in the first and third Tests for the Lions last summer, was one of eight 2009 Lions named in Martin Johnson's England squad this week.
England haven't claimed the Six Nations Championship since their World Cup winning year of 2003 but Monye is confident that could be about to change.
"We definitely should go into it thinking that we can win it," said Monye.
"We have very high expectations of ourselves and just have to have the confidence to win it.
"We have players who are playing well for their teams domestically and we just need them to transfer that form onto the international stage.
"It will be difficult but I think it is definitely possible. All we have to do is have the belief that we can.
"We have a very good coaching staff and have to have belief within the playing staff that we can win it."
England go into Europe's premier international tournament on the back of another disappointing autumn series after a narrow win over Argentina was sandwiched by convincing defeats to Australia and New Zealand.
Former Lions skipper Johnson and his coaching staff have since come under increasing scrutiny but Monye insists that England have the right team in place to take them forward.
"There's nothing wrong with the coaches at all," Monye said.
"It was a frustrating series for us as a team and it was frustrating for me on a personal level in the second game.
"It was good for me to have the experience of playing against New Zealand. I had to play two games at full-back but when I was out on the wing I was much more comfortable.
"The criticism made us stronger as a unit and we tried not to get involved.
"It's not nice hearing it but obviously the management are going to be the first ones in the firing line when things go wrong."