The Real Madrid centre-back made his international debut 14 years ago in a friendly against China.
The 33-year-old was part of the Spain sides which lifted the 2010 World Cup, Euro 2008 and Euro 2012 titles.
He took over the Spain captaincy in 2016 after goalkeeper Casillas' final match and will set a new record next month if he plays against either Norway or Sweden.
He is now only nine caps short of the European record held by Italian stopper Gianluigi Buffon (176) and 17 adrift of Egyptian Ahmed Hassan's world record of 184.