Yes, Alfredo Di Stefano did play for Colombia, representing the national team in four games but scoring no goals way back in 1949.
Di Stefano ended up representing Colombia following a general strike back in Argentina in 1949, that saw much of the professional football league grind to a halt.
Seeking refuge and eager to continue his career, Di Stefano opted to move to Colombia signing with Millonarios Bogota. Di Stefano would stay in Bogota for three and a half seasons, winning three titles and scoring a total of 120 goals in 131 games for the club.
It was during this period that he was invited to play for the Colombian national team. It is important to remember though that the rules surrounding international selection were much more relaxed back then and more importantly, the Colombian leagues and national team were not formally recognised by FIFA at the time, making the appearances somewhat "unofficial."