The footballing legend broke the deadlock towards the end of the first-half with a sweet finish after combining smartly with former Manchester City star Nicolas Otamendi on the edge of the penalty area.
Lionel Messi marked his 1,000th senior game with a goal to help see Argentina through to the World Cup quarter-finals by beating Australia.
Australia threatened a fightback at the Ahmad Bin Ali Stadium after Craig Goodwin's deflected shot halved the deficit, but a superb last-ditch tackle from Manchester United's Lisandro Martinez denied Aziz Behich what would have been an equaliser in the 80th minute.
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