The Barcelona midfielder will start against Australia to become the ninth player to reach 100 caps for the reigning European champions
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Iniesta made his debut for Spain's national side in a friendly against Russia in May 2006 and was part of the team that won Euro 2008, 2010 World Cup and Euro 2012.
The highlight of his international career was arguably the goal he scored in the World Cup final at South Africa 2010 as he helped Spain to a 1-0 win over Netherlands after extra-time.
Iniesta is the ninth player to reach the 100-cap mark, following in the footsteps of Iker Casillas, Xavi, Andoni Zubizarreta, Sergio Ramos, Alonso, Fernando Torres, Raul and Carles Puyol.
The 30-year-old has taken part in all of Spain's games at this summer's World Cup, though after two defeats this will be his final outing in Brazil.