Only two countries have won back-to-back World Cups: Italy in 1934 and 1938 and Brazil in 1958 and 1962. On Wednesday, Chile made sure that Spain will not be the third country to do so.
Chile eliminated the defending champions with a 2-0 win in a Group B match at Maracana Stadium in Rio de Janeiro.
Spain suffered its second loss of the tournament after being dominated by the Netherlands last week, 5-1.
Chile, Netherlands in knockout round
The win assured Chile and the Netherlands of spots in the Round of 16, also known as the "knockout round." Both countries have six points, the most in Group B, but the Dutch are ahead on goal difference with plus-five to Chile's plus-two.
Chile scored both of its goals in the first half. Eduardo Vargas tricked Spain's goalie Iker Casillas and shot into an unguarded net in the 20th minute. Charles Aranguiz doubled the lead in the 43rd minute when the ball landed at his feet after Casillas punched out a free kick.
Spain has been outscored 7-1 in this year's in the World Cup.
Before the game, more than 100 fans of Chile stormed the Maracana media center in hopes of getting into the stadium. Security officers surrounded the group and led many of them away.
Earlier Wednesday, the Netherlands added three points with a 3-2 win over Australia in Porto Alegre. Australia, the lowest-ranked team in the tournament, took a 2-1 lead in the 51st minute with a goal by Mile Jedinak, but the Dutch overpowered the Aussies with two goals in the next 15 minutes.
In a Group A match, Croatia routed Cameroon in Manaus, 4-0. The must-win game for both teams kept Croatia's World Cup dreams alive and eliminated Cameroon. Croatia lost its first game to Brazil, 3-1.
Legendary Brazilian speaks
On Wednesday, Brazilian football legend Pele' said there is too much pressure on Brazil's superstar striker, Neymar, to win a sixth World Cup for his country. Pele' won World Cups in 1958, 1962 and 1970 and is Brazil's all-time leading goal scorer.
"It's a little bit different, you know, but it's almost the same because it's the big star from the Brazilian team now," Pele said at a football clinic in Rio de Janeiro. "But In 1958, I was 17 years old, now Neymar is 22 and plays in Europe. But I think there is too much pressure on him because everybody expects Neymar to win the World Cup for Brazil. But the one who wins the World Cup is the team, not the player. He's a good player, but it's too big a responsibility to expect him to win the World Cup."
Pele' also said he hopes his country can avoid a repeat of the 1950 World Cup, the only other time Brazil has hosted the event. That year, Brazil suffered a heartbreaking loss to Uruguay in the championship game.
"As I told you, this is a game, and I hope I don't have the same experience as that," he said. "I saw my father was crying, I saw my father cry. I don't want my sons, my kids to see me cry at this World Cup because Brazil lost. I want to cry out of happiness!"
Brazil is the consensus favorite to win the tournament but has struggled. The Brazilians beat Croatia with the help of two generous calls by a referee and battled Mexico in a scoreless draw.
Brazil and Mexico have the most points in Group A with four, but Brazil is ahead on goal difference. Croatia is right behind with three points.
In other news, Russian President Vladimir Putin plans to be in Brazil for the end of the World Cup. He will take part in a handover ceremony after the tournament championship game on July 13. Russia will host the next World Cup in 2018.
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2014 Brazil World Cup Moments, June 18, 2014
Mexico's Rafael Marquez (left) fights for the ball with Brazil's David Luiz during their 2014 World Cup Group A soccer match at the Castelao arena, in Fortaleza, June 17, 2014.
Algerian soccer fans watch their team's World Cup soccer match with Belgium on a large screen, in Algiers, June 17, 2014.
South Korean rapper Psy performs during a public screening before the 2014 World Cup Group H soccer match between South Korea and Russia, in Seoul, June 18, 2014.
A baby wears a wig while playing among Brazilian soccer fans watching the match between Brazil and Mexico during the World Cup 2014, in Manaus, June 17, 2014.
Russia's Igor Akinfeev fumbles the ball to concede a goal to South Korea's Lee Keun-ho during their 2014 World Cup Group H soccer match at the Pantanal arena, in Cuiaba, June 17, 2014.
Russia's Alexander Kerzhakov (No. 11) is seen in action before scoring the goal against South Korea during their 2014 World Cup Group H soccer match at the Pantanal arena, in Cuiaba, June 17, 2014.
South's Korea's national soccer players pile on top of teammate Lee Keun-ho as they celebrate his goal against Russia during their 2014 World Cup Group H soccer match at the Pantanal arena, in Cuiaba, June 17, 2014.
A girl wearing the Brazilian flag runs through the slum of Varjao on the outskirts of Brasilia, ahead of the 2014 World Cup Group A soccer match between Brazil and Mexico, June 17, 2014.