The first leg will be played in Nairobi on February 14 with the return leg slated for February 21.
The aggregate winner will proceed to the group stage of the competition, and assured of at least Sh30 million in prize money.
The Kenyan champions were relegated to the Confederation Cup after being bundled out by Algerian side CR Belouizdad following a 8-1 aggregate thrashing in the Caf Champions League first round.
On the other hand, Napsa Stars proceeded to the play-offs on away goals rule after a 1-1 aggregate score against UD Songo of Mozambique.
Napsa Stars is home to former Gor Mahia players Shaban Odhoji and Timothy Otieno as well as another Kenyan Andrew Tololwa, formerly of Mathare United and AFC Leopards.
His six-year stint saw him establish himself as one of the best foreign talents not only at Zesco United but also in the Zambian league. He went on to win five Super League titles, three Absa Cups, and two Charity Shields.
His great abilities also saw Zesco United establish themselves as regular competitors in the Caf Champions League and in the Confederation Cups.
Odhiambo was part of the general Timu ya Ziko squad that struggled in the 2019/20 season, failed to defend the Super League title and finished fifth. They ended up missing on the continental slots after participating in the last eight years.