The Palancas Negras, who made their debut at the 2006 finals in Germany, put up a good fight in Cotonou, but were edged out 3-2 by the hosts thanks to a brace from Razak Omotoyossi.
Khaled Adenon fired the Squirrels ahead after just two minutes, before Flavio Amado (12) pulled the visitors level.
The score remained at 1-1 until the 52nd minute when Omotoyossi restored his side's advantage and then he stretched the lead even further with his 66th-minute effort.
Manuel Morais (78) pulled one back for Angola, but it proved only a consolation as Benin assured themselves a first-place finish in Group Three.
Michel Dussuyer's team now have 12 points, five more than the Angolans, who must win their last game against Niger and hope results elsewhere go their way if they are to finish as one of the eight best runners-up in the 12 group zone.
The other game in the pool saw the Mena claim a stunning victory over Uganda with three goals in the final 13 minutes enough to secure victory in Niamey.
David Obua's 34th-minute goal looked to have earned his side all the points, but the hosts had other ideas scoring through Issoufou Dante (77 and 88) and Kamilou Daouda (89) to complete a memorable first win in the qualifiers for Niger.
In Group Two, Zimbabwe and Guinea had to settle for a share of the spoils in a goalless draw in Harare.
A point apiece was not the ideal result for either side, who must now rely on victories on the final day as the only way of guaranteeing qualification to the final phase. Guinea host Kenya and Zimbabwe play away at Namibia.
Gabon threw Group Five wide open by overcoming Lesotho 3-0 in Bloemfontein.
Goals from Bruno Ecuele, Roguy Neye and Bruno Mbanagoye were enough to help the Gabonese move into second place on eight points, ahead of the much fancied Ghana, who lost 1-0 to leaders Libya on Friday.
However, the Black Stars have the easier final game against strugglers Lesotho, while Gabon host Libya.
Ivory Coast moved a step closer to qualification in Group Seven despite only drawing 1-1 against Mozambique in Maputo.
Bakari Kone (47) fired the Elephants ahead, but the lead lasted just seven minutes as Miro earned his side a fighting draw.
The Ivorians move to nine points, three clear of closest challengers Madagascar, who claimed a narrow 1-0 win over Botswana.
Praxis Rabemananjara (18) scored the only goal in Antananarivo and the islanders will now have to win their final game in Abidjan to have any chance of progression.
In Brazzaville, Wilfrid Endzanga scored an 88th-minute winner as Congo stunned Mali 1-0 to join their opponents at the summit of Group 10.
Both sides now have nine points, three more than Chad, and should progress to the final round of qualifying.
Finally in Group 12, Mohamed Aboutreika's goal on the half-hour mark guided African champions Egypt to a hard-fought 1-0 win over the Democratic Republic of Congo in Kinshasa.
The Pharaohs now have 12 points and are guaranteed a place in the final qualifying stage, while DR Congo must battle with Malawi to try and go through as runners-up.
In Group 10, Chad moved within three points of leaders Mali alongside second-placed Chad with two games remaining after recording a 2-1 win over Sudan.by espnstar.com
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