Last week La Liga announced plans to play one match a season in the United States as part of a partnership with Relevent, an multinational sports and entertainment group wanting to promote the sport across North America.
According to 'AS', Messi and the 19 other captains will oppose the move on Wednesday at the Spanish Footballers' Association - the President of which, David Aganzo, will deliver their stance against league officials following claims that they, alongside the Spanish Football Federation, were not informed of the proposal.
It is understood that all 20 captains, including Champions League winner Sergio Ramos, will sign the stance.
The plans could mean that La Liga sees an overseas game played as early as this season, though arrangements are yet to be made.
La Liga have continuously being making efforts to expand in recent years, like the Premier League. The league's international development manager, Oscar Mayo, spoke of the proposal in a statement.
"Joining with Relevent to create La Liga North America is a major milestone in our international expansion strategy.
"This agreement ensures not only a bright future for soccer in North America, but also for La Liga and our clubs."