Domestic media build-up to the first round, first leg at Nelson Mandela Bay Stadium in Indian Ocean city Port Elizabeth was dominated by talk of the Buccaneers going all the way this year and winning the title a second time.
But dreams of emulating the 1995 team and conquering the continent were all but extinguished by the unheralded Angolans and Pirates will have to score at least three goals in Luanda early next month to have any hope of surviving.
Libolo, appearing in the premier Pan-African club competition for only the second time, raced into an early two-goal lead and struck again midway through the second half before Pirates got a stoppage-time consolation.
Maieco Henrique punished comical defending to open the scoring on 12 minutes with a close-range shot and struck again soon after when he picked up a headed clearance, raced through unopposed and unleashed a thunderbolt.
Pirates' defence was all at sea again after 63 minutes and Camara swept a loose ball inside the box past stand-in goalkeeper Senzo Meyiwa before Rooi Mahamutsa pulled one goal back.
It was a result no one in South Africa foresaw, and a shattering blow for long-serving club chairman Irvin Khoza, who wanted continental glory after winning all the domestic trophies during the past 18 months.
Just one week after winning the Africa Cup of Nations against the odds, Zambia had further cause for celebration as Power Dynamos travelled to Madagascar and thumped Japan Actuel 5-1 in Antananarivo.
Mulenga Mukuka and Felix Nyanda scored twice each and Simon Bwalya was also on target for the visitors, who led 1-0 at half-time, while Rindra Rakotondrabe was the lone Actuel marksman.
Debutants Platinum of Zimbabwe also displayed impressive away form to triumph 4-2 against Green Mamba in Swaziland with Donald Ngoma scoring twice and Allan Gahadzikwa and Sadiki Ali once each.
Former Wigan Athletic striker Amr Zaki struck in the closing stages to salvage a 1-1 draw for five-time champions Zamalek of Egypt after hosts Young Africans of Tanzania had taken a first-half lead through Hamisi Kiiza.
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