After clashing in a qualifier last year, the clubs were brought together again when the group draw was made in Cairo on Wednesday.
The Kinshasa outfit triumphed on away goals in the 2016 season only to be kicked out of the premier African club competition for fielding a suspended player.
Sundowns took full advantage of a second chance by going on to defeat Zamalek of Egypt in the final and lift the trophy for the first time.
V Club won the competition in 1973 when it was called the African Cup of Champions Clubs, had an exclusively two-leg format and offered no prize money.
Another former winner of the competition, Esperance of Tunisia, and impressive qualifiers Saint George of Ethiopia complete Group C.
The “Saints” won all four qualifiers, scoring eight goals and conceding none, and boast the leading Champions League scorer this season in five-goal Saladin Said.
Sundowns host Saint George in matchday 1 during May and coach Pitso Mosimane will be wary of facing Ethiopian opposition.
The former national team striker was sacked as South Africa coach after a home draw with Ethiopia in a 2014 World Cup qualifier.
Bitter Sudanese rivals Al Hilal and Al Merrikh were placed in Group A with Etoile Sahel of Tunisia and Ferroviario Beira of Mozambique.
Record eight-time African champions Al Ahly of Egypt are in Group D with Wydad Casablanca of Morocco, Coton Sport of Cameroon and Zanaco of Zambia.
Zamalek were placed in Group B with USM Alger of Algeria, Al Ahly Tripoli of Libya and CAPS United of Zimbabwe, shock qualifying conquerors of TP Mazembe of DR Congo.
No west African club qualified, only the third time this has occurred since groups were introduced 20 years ago.
The west is the second most successful region in CAF club competitions with 26 titles — 49 less than teams from the north.
Group fixtures run from May 12 to July 9 followed by quarter-finals, semi-finals and the final over two legs.
Champions League format changes this year include expanding the group phase from eight clubs to 16 and hefty prize money increases.
Qualifiers for the mini-league stage are guaranteed $550,000 (505,000 euros) and the champions receive $2.5 million.
CAF Champions League group draw made in Cairo Wednesday:
Etoile Sahel (TUN), Al Hilal (SUD), Al Merrikh (SUD), Ferroviario Beira (MOZ)
Zamalek (EGY), USM Alger (ALG), Al Ahly Tripoli (LBA), CAPS Utd (ZIM)
Mamelodi Sundowns (RSA, holders), Esperance (TUN), V Club (COD), Saint George (ETH)
Al Ahly (EGY), Wydad Casablanca (MAR), Coton Sport (CMR), Zanaco (ZAM)
May 12-14, May 23-24, June 2-4, June 20-21, June 30-July 2, July 7-9
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