He moved to the United States from his native Ecuador in 1980 to attend Chapman University, and later played two seasons with the Los Angeles Lazers in the Major Indoor Soccer League.

In 1990, Zambrano was an assistant coach to Rildo Menezes (Ex-Santos of Brasil and New York Cosmos) with the California Emperors in the American Professional Soccer League.

Following his work with the LA Salsa Zambrano was hired as director by the Mission Viejo Pateadores, one of the United States Top Soccer Academies.

Zambrano coached the Western Division All Star Team and the Galaxy 97/98 achieved the record for most consecutive regular season wins (12).

[4] Deportivo Pereira during the second semester of 2012 broke the record of points obtained in a single season by any Colombian professional soccer team since the installment of short tournaments.

During the first tournament of 2013, after a good start a string of injuries to main players coincided with a failure to secure a victory in four consecutive games and left the team out of the group of 8.

In April 2013, the president and owner of Deportivo Pereira Alvaro Lopez Bedoya, opted to relieve Octavio Zambrano of his coaching duties and assigned him those of manager and technical director.

In June 2014, Zambrano became a TV game analyst for the Ecuadorian International Network Ecuavisa, as a member of Codigo Mundial, the highest-rated World Cup show in Ecuadorian TV; his participation in this show opened the door to take the reins of El Nacional, getting the club out of the relegation zone and into the group of 6, trying to secure a berth into Conmebol's International Tournaments: Copa Sudamericana and Copa Libertadores.