As a teenager, Madero was drawn initially to basketball, but decided on football when it became clear he had the talent to make it in the professional league.

He played for Boca Juniors and Huracán but he came into his own with the Estudiantes de La Plata team that won several national and international titles between 1967 and 1970.

Madero provided firmness but also elegance as a defender, playing alongside the less-polished Ramón Aguirre Suárez.

[citation needed] Madero and fellow player Carlos Bilardo retired after graduating as Medical Doctors.

Madero was also head of the Sports Medicine program in the Buenos Aires branch of the Pontifical Catholic University of Argentina.