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2006 FIFA World Cup
Busacca was chosen to be a referee at the 2006 FIFA World Cup in Germany.

While refereeing a World Cup match between Ukraine and Spain, Busacca made a decision against Vladislav Vaschuk, giving the player a red card and awarding a penalty kick against Ukraine in the 47th minute of the match. Multiple angles of the infraction showed no physical contact inside the penalty area, preceded by a tug on the pants of Fernando Torres in the penalty area by Vladislav Vaschuk. David Villa of Spain slotted home the resulting penalty against Ukrainian keeper Oleksandr Shovkovsky. The refereeing decision was criticized by numerous fans. Observers point out that subsequently, in a similar situation involving Ukraine's Andriy Voronin and the Spanish defence, the referee decided no foul had occurred.

On March 24, 2007, Busacca was appointed to referee a UEFA Euro 2008 qualification match between Spain and Denmark at the Santiago Bernabéu, Madrid.

In the match, he sent off Danish defender Niclas Jensen after 20 minutes in the first half. Till that point the game had been dominated by the Danes. The red card changed the course of the game, and Spain won 2-1. Danish coach Morten Olsen was also sent off in the match.

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