Burgnich was also a pillar of the Italian national team for more than a decade. He represented Italy at the 1960 Summer Olympics in Rome, where they finished in fourth place. He made his senior debut on 10 November 1963, in a 1–1 home draw against the Soviet Union, and subsequently became a permanent fixture in the team's line-up, wearing the number 2 shirt, and later helping the national side win their first ever and currently only European Football Championship title in 1968, on home soil. He was also on Italy's roster for the 1966 World Cup, as well at the 1970 World Cup, where they reached the final, only to lose 4–1 to Brazil. In the memorable semi-final match against West Germany, often colloquially known as the "Game of the Century", Burgnich even managed to score a goal, helping his team to overcome the Germans 4–3 following extra time. He also took part in the 1974 FIFA World Cup with Italy. In total, he represented the "Azzurri" 66 times between 1963 and 1974, scoring twice.