The World Cup and UEFA Champions League winner will appear in Australia's domestic competition next season as part of the deal taking him to New York City FC
Villa, who is in camp with Spain ahead of the FIFA World Cup, will complete a guest stint with Melbourne City before linking up with New York City as they make their MLS debut in 2015.
The 32-year-old striker became the first player to sign with New York City on Monday, after announcing he was leaving Atletico Madrid the day earlier, and will join Melbourne City on a 10-game contract to keep fit in the second half of this year.
With City having purchased Heart in January, Thursday's announcement underlined how different the Australian club's future could be with Abu Dhabi ownership, who also control Premier League champions Manchester City.
Villa scored 13 goals for Atletico as the Madrid-based club won their first La Liga title in 18 years last season, while he also started in the UEFA Champions League final defeat to Real.
The former Valencia and Barcelona forward is Spain's all-time leading goal-scorer with 56 strikes in 94 appearances and will be a key man for Vicente del Bosque, as the Europeans attempt to defend their world title in Brazil.
Villa will arguably become the best player to play in the A-League as he will arrive at City still at the top of his game, compared to former Sydney FC marquee signings Alessandro Del Piero and Dwight Yorke, who arrived at the ages of 37 and 33 respectively.
As part of their re-branding to Melbourne City, the team will wear predominantly white shirts next season encorporating some blue, having been blocked from changing their home colours to all sky blue following objections from Sydney FC.