John Obi Mikel, Obafemi Martins, Obinna Nsofor and Osaze Odemwingie also scored from the spot to give the 'Super Eagles' a 100 percent success rate from five kicks. Thomas Nyirenda was the unconsolable Zambian at the end after Enyeama saved his kick - the seventh of the shootout - and Nigeria scraped through despite having Onyekachi Apam sent off during extra time.
The ultra-negative last quarter-final of the biennial African football showcase was a massive disappointment after victories for Ghana, Algeria and Egypt in thrillers.
Defending champions Egypt made the penultimate stage a few hours before Nigeria thanks to a 3-1 extra-time triumph over Cameroon with 170-cap midfielder Ahmed Hassan scoring twice for his side and once for his opponents.
Back in the knockout phase of the competition for the first time since 1996, Zambia had to make two enforced changes from the side that defeated Gabon to reach the quarter-finals as shock Group D table-toppers. Defender Chintu Kampamba and midfielder Rainford Kalaba collected two yellow cards each in the mini-league stage and young French coach Herve Renard drafted in Hichani Himonde and William Njobvu.
Nigeria retained the starting line-up from their final pool match against Mozambique that delivered an ultimately convincing 3-0 win and justification that they could go far in the tournament after a sluggish start. Jubilant that his pre-tournament promise of a quarter-finals place had been met, Renard saw the game as a chance to embellish his reputation amid reports that he desires a more attractive African coaching post.
Rival coach Shaibu Amodu is 10 years older at 51 and under constant stress from public and media criticism despite just one competitive loss since taking charge of the national team a third time a couple of years ago.
The countries had come face to face four previous times in the Nations Cup with Nigeria winning two and Zambia one after a goalless first meeting in Ghana 32 years ago. And after a goalless first half in this central Angolan town it was hard to fathom who would prevail this time and book a semi-finals date with the Black Stars of Ghana in Luanda on Thursday afternoon.
Chelsea midfielder Mikel ended a lot of cagey early combat with a sweetly struck drive after some slick passing, but Kennedy Mweene dived swiftly to his left and pushed the ball away with a strong one-hand save. Zambia became more adventurous as time passed and after Enyeama rose to grasp a deep, dangerous cross, striker James Chamanga just failed to connect with a threatening ball across the six-yard box.
It was not a half for the faint hearted with some borderline tackling and by the break Zambians Felix Katongo, Himonde and Joseph Musonda had been shown yellow cards by the Egyptian referee. The second half began as the first ended with more than fouls than thrills for a less-than-capacity crowd in the 20,000-seat venue and Apam joined the yellow-card offenders via a rash tackle on Chamanga.
Midway through the half and finally the crowd had something to cheer as Yusuf Mohammed cleared off the line to rescue Nigeria and hesitant captain Yakubu Aiyegbeni squandered a close-range opportunity at the other end. It was painful watching the closing stages of regulation time as two teams far more concerned with not losing than winning rarely mounted threatening attacks and full-time came without a goal.