Tanzania-born midfielder Mbwana Samata saved the blushes of Les Corbeaux with the match winner on the half-hour mark.
The victory confirms Mazembe’s dominance over their bitterest rivals in meetings between the two sides since November 2012, and also hands them the bragging rights over in their first ever clash at the continental level.
After several unsuccessful attempts at breaking the deadlock, Mazembe eventually broke through on 62 minutes through Samata to earn them their first win at this stage.
Earlier on Saturday, Zamalek managed a 2-1 win over Al Hilal of Sudan in Cairo.
The results open the group with all four times tied on three points after two games.
In Setif, Sfaxien came from behind to snatch a vital draw against Entente Setif to maintain their place at the summit of Group B.
El Hedi Belameiri fired the hosts into the lead after 12 minutes, but Sfaxien captain Ali Maaloul made certain of a point for the visitors with the equalizer on the stroke of half time.
In the other Group A match on Saturday, Ahly Benghazi handed Esperance their second successive loss at the group stage, beating them 3-2 in Sfax.
Sfaxien sit atop with four points, same as Entente Setif with Ahly Benghazi – 3 points and Esperance pointless in that order.
24-05-2014 Zamalek (Egypt) 2-1 Al Hilal (Sudan)
25-05-2014 TP Mazembe (DR Congo) 1-0 AS Vita (DR Congo)
24-05-2014 Ahly Benghazi (Libya) 3-2 Esperance (Tunisia)
25-05-2014 Entente Sétif (Algeria) 1-1 CS Sfaxien (Tunisia)
Win saw Mazembe continue to enjoy their superiority over their archrivals from Kinshasa after picking a fourth successive win in all competitions over the latter since November 2012.