Diego De Souza scored with a fierce shot in the 28th minute in the Bombonera to lift Defensor into the quarter-finals 3-2 on aggregate.
That set up quarter-finals of Cruzeiro verus Sao Paulo, Caracas verus Gremio, Estudiantes verus Defensor and Palmeiras verus Nacional.
The first legs are next Wednesday and Thursday with the return legs a week later.
Brazilian clubs have dominated the competition so far, with four teams through to the last eight.
The Copa Libertadores finals are scheduled for July 1 and 8.
Boca have won the title four times since 2000 and were aiming for a record-equalling seventh crown.
Defensor have never won the competition and equalled their best performance by reaching the quarter-finals.
Juan Roman Riquelme played for Boca after recently returning from almost six weeks out with a foot injury.
Riquelme, Boca’s playmaker, looked short of match fitness and Defensor’s counterattacks worked well.
Boca’s best chance came after 43 minutes when Sebastian Battaglia’s header was tipped to safety by Defensor goalkeeper Martin Silva.
The Argentine club became increasingly desperate as the game wore on but could not break down the disciplined Defensor rearguard.
Defensor will face another Argentine club, Estudiantes, for a place in the semi-finals. — AP
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