The meeting between Messi's Argentina and Ronaldo's Portugal in Geneva is one of a number of attractive friendly internationals on an evening when France play Brazil and Germany meet Italy in two other classic encounters.
Meanwhile world champions Spain start their international year with a game against Colombia, while England are up against Denmark in Copenhagen.
Among some two dozen games, losing World Cup finalists Netherlands entertain Austria, Croatia play Czech Republic while Euro 2012 co-hosts Poland meet Norway.
Fellow hosts Ukraine play Romania on Tuesday in a four-nation tournament in Cyprus, where the home side are up against Sweden. The final and third-place play-off take place Wednesday.
World player of the year Messi is vying with Ronaldo for the top goalscorers' crown in Spain, and both will be out to show who is the more effective for their countries in Geneva.
"For me, it is not just about Ronaldo against Messi, but above all about Portugal against Argentina - individual duels are for the fans," said Portugal coach Paulo Bento who succeeded Carlos Queiroz in September.
Portugal are on a high after thrashing world champions Spain 4-0 in November and are keen to start the year well ahead of what could be a tough task to qualify for Euro 2012 where Norway and Denmark are also looking strong.
"We want to win and play well. It is an important game to prepare the key qualifier against (next opponents) Norway in June," Bento said.
Argentina Sergio Batista, who took over from Diego Maradona after last year's World Cup, may use the game to test new players ahead of the Copa America on home soil in July.
"This is a good moment to try out some youngsters," he said.
France face Brazil in the Stade de France evoking memories of the 1998 World Cup final won by the hosts.
France's last meeting with Brazil was a 1-0 win in the 2006 World Cup quarter-finals, and coach Laurent Blanc is eager to see how his side now measure up against the five-time world champions as they continue to put last year's World Cup debacle behind them.
"For me, Brazil's the home of football and they've produced so many talented players over the years," Blanc told the FIFA website.
"We don't get that many chances to play against them, either in friendlies or in the World Cup."
"The players are well aware that this is a unique opportunity, and my guess is that there were a lot more French players waiting on the announcement of the squad than usual.
"Taking on one of the top two teams in the world in front of our own fans could help the team grow in confidence."
Germany host Italy in Dortmund, hoping to avenge defeat to the Italians at the ground in the 2006 World Cup semi-finals.
Germany have a negative record (7 wins, 8 draw, 14 defeats) against Italy and have lost their last three games against the Azzurri - their last victory going back to June 1995 when they won 2-0 in a friendly in Zurich.
Meanwhile Spain will be aiming to find their feet after losing 4-1 against Argentina and 4-0 in friendlies in the autumn.
"We have to be aware that we should give the best image possible. I do not want a repeat of what happened against Portugal. Colombia are a good team, nearly all of their players are playing in European leagues," coach Vicente del Bosque said.
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