The Juventus midfielder is joined by goalkeeper Claudio Bravo, who will have to work with an inexperienced back line.
Arturo Vidal was named in Chile's 30-man provisional FIFA World Cup squad despite undergoing knee surgery last week.
The Juventus midfielder had arthroscopic surgery on the lateral meniscus of his right knee in Barcelona in a bid to be fit for the upcoming showpiece in Brazil.
And despite his return date being unknown, Vidal was picked in coach Jorge Sampaoli's squad on Tuesday, alongside fellow star Alexis Sanchez.
The pair will be expected to inspire Chile as they battle 2010 finalists Spain, the Netherlands and Australia in a difficult Group B.
Goalkeeper Claudio Bravo, also captain of his country, and Valencia forward Eduardo Vargas will also have a key role to play.
Vargas scored five goals in qualifying as Chile finished third in the South American section after winning nine of their 16 matches.
There was no place in the squad for Monterrey forward Humberto Suazo, while Fiorentina midfielder David Pizarro also missed out.
But defender Miiko Albornoz – who was born in Sweden and played for their Under-21 team as late as last year – was included despite only having one Chile cap to his name.
Chile open their World Cup campaign with a clash against Australia on June 13.
Squad in full:
Goalkeepers: Claudio Bravo (Real Sociedad), Paulo Garces (O'Higgins), Johnny Herrera (Universidad de Chile), Cristopher Toselli (Universidad Católica)
Defenders: Miiko Albornoz (Malmo), Enzo Andia (Universidad Catolica), Marcos Gonzalez (Union Espanola), Gonzalo Jara (Nottingham Forest), Gary Medel (Cardiff City), Eugenio Mena (Santos), Jose Rojas (Universidad de Chile)
Midfielders: Charles Aranguiz (Internacional), Jean Beausejour (Wigan Athletic), Carlos Carmona (Atalanta), Marcelo Diaz (Basel), Matias Fernandez (Fiorentina), Jose Pedro Fuenzalida (Colo Colo), Felipe Gutierrez (Twente), Pablo Hernandez (O'Higgins), Mauricio Isla (Juventus), Rodrigo Millar (Atlas), Francisco Silva (Osasuna), Jorge Valdivia (Palmeiras), Arturo Vidal (Juventus)
Forwards: Gustavo Canales (Union Espanola), Fabian Orellana (Celta), Esteban Paredes (Colo Colo), Mauricio Pinilla (Cagliari), Alexis Sanchez (Barcelona), Eduardo Vargas (Valencia)