The defending European champions are using the match at St. Gallen to prepare for Tuesday's Euro 2012 qualifier against Liechtenstein.
Spain's recent record in friendlies hasn't impressed, as it comes off a 2-1 defeat to the Azzurri that dropped it from FIFA's No. 1 ranking for the first time since its Word Cup win in South Africa last year.
And the recent run of ill-tempered club matches between Barcelona and Real Madrid have taken their toll, with 14 players in the 24-man squad coming from those two teams.
Much has been made of Madrid-Barcelona players making peace after their last meeting ended in a brawl, with coach Vicente del Bosque expecting relations to remain intact, especially as the Spanish coach believes that dressing room harmony is a key ingredient to Spain's success.
''We talk about things just as we do every time we gather, and the coach is also here to help smooth things over. There was never any big problem after the clasicos,'' midfielder Xavi Hernandez, who will match Raul Gonzalez's 102 appearances if he plays, told reporters on Thursday.
The Barcelona captain said he spoke with his Madrid counterpart Iker Casillas following the series to clear the air.
''We're people who like football and we want to be in a good environment with good ambiance. We want Spanish football to be healthy - we won the World Cup and the European Championship, we're in the best moment of our history.''
Del Bosque has called up three uncapped players to join newcomer Thiago Alcantara, with the Barcelona midfielder among six players who led Spain to the under-21 title in June. The usual threats of Fernando Torres, David Villa, David Silva, Xavi Hernandez, Andres Iniesta and Cesc Fabregas are all in the team.
''It's a good signal that all six of us are here in the team, it demonstrates there's a very good generation of players coming up and that they are in the national team,'' said new Chelsea signing Juanma Mata, the U21 captain. ''The coach has shown confidence in all of these players.''
While Spain has struggled in friendlies - it lost to Argentina and Portugal by a combined 8-1 score since South Africa - in European qualifying it has been perfect, winning all five of its games to lead the Czech Republic by six points atop Group I.
Spain and Chile met at the World Cup last year with the Spanish winning 2-1 to finish first in their group.
Chile has never beaten Spain in eight previous matches, with Spain winning three straight and seven overall since their first meeting in 1950.
Chile coach Claudio Borghi has already said he will start Barcelona forward Alexis Sanchez and Fabian Orellana in attack at AFG Arena.
''It's always important to win but we're looking for something else here, for a clear system of play, a system we can play well with,'' said forward Arturo Vidal, whose team has lost only one of its last 13 matches and is coming off a 1-1 draw against France. ''It's always a dream to play against the world champions.''
While Spain travels to Logrono for Tuesday's game, Chile will also visit Spain to play Mexico in Barcelona on Sunday.