Highly motivated by these promising results indicating that PCI and PCII impart enantioselectivity in a visible-light mediated energy-transfer-catalyzed reaction, we wanted to further explore their performance as photoredox catalysts. To study this ability, we were especially interested in a recently published example of a chiral photoredox-catalyzed Minisci reaction (Table ). The reported example utilized 2 mol% of 4CzIPN along with 10 mol% of a chiral phosphoric acid at 15 °C to construct chiral heterobiaryls 17 in good yields with excellent ee and diastereoselectivity (entry 1). We chose this example to test whether the novel bifunctional catalysts can replace the dual catalytic system and fulfill the role of both chiral phosphoric acid and photocatalyst in an enantioselective fashion in this photoredox-catalyzed reaction. By subjecting both PCI and PCII to the literature reported reaction conditions, albeit at a slightly higher temperature (room temperature), we were delighted to find that without any optimization, an enantioselectivity of 21% with a yield of 33% was achieved with PCI (entry 4). Using only 4CzIPN gave no product formation (entry 2), indicating that the phosphoric moiety of PCI is necessary for the reaction. Indeed, by adding in 20 mol% racemic phosphoric acid rac-PA, racemic product 17 could be obtained with 4CzIPN in low yields (entry 3).