Underdogs Benin will be pinning their hopes on Paris Saint-Germain star Stephane Sessegnon when they take on fellow minnows Mozambique.
After being drawn against giants Egypt and Nigeria, both sides need to win to stand a realistic chance of progressing to the knock-out stages.
Neither team has previously won a game at the Africa Cup of Nations.
Mozambique's Dutch coach Mart Nooij is confident his side can get past the group stages.
"In Angola there will be 14 teams playing away which makes the refereeing and conditions similar for all the teams," he said.
"I would be delighted with a quarter-finals place."
The Dutchman will be looking to build on an impressive qualifying campaign which saw his team achieve an unbeaten home record, including a draw with two-time Nations Cup winners Nigeria.
Benin's last six games in the Nations Cup have ended in defeat.
Michel Dusseyer's side will turn to FC Metz striker Razak Omotoyossi for goals, but Sessegnon will be expected to provide key strength in midfield.
"When you talk of Benin football his name immediately comes to mind," said Dusseyer of Sessegnon.
"There are other good players in the squad like Razak [Omotoyossi], but Stephane has taken his image to another level which is good for the team."
Benin's young squad came second to Ghana in their qualifying group.