The tie ended 1-1 on aggregate with penalty needed to decide the winner.
Rivers United levelled the contest following Fortune Ominiwari’s 42nd minute strike.
They were however unable to add to their advantage despite dominating the game for long spell.
Cyril Olisema missed Enyimba’s first kick, but Enyimba recovered to score their next five kicks.
Kunle Odunlami and Isreal Emmanuel missed from the spot for Rivers United.
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