Visible light irradiation of a benzonitrile solution containing C70 and an NADH analogue, 4-tert-butyl-1-benzyl-1,4-dihydronicotinamide (t-BuBNAH), results in efficient formation of the tert-butylated anion (t-BuC70-) accompanied by the oxidation of t-BuBNAH to BNA+. The transient formation of C70*- (λmax = 1374 nm) has been detected, accompanied by the decay of the triplet - triplet absorption band of 3C70* at 960 nm in laser flash photolysis of the t-BuBNAH-C70 system. The initial electron transfer from t-BuBNAH to 3C70* to produce t-BuBNAH*+ and C70*- is followed by fast C - C bond cleavage in t-BuBNAH*+ to give t-Bu* which is coupled with C70*- to yield t-BuC70-. The limiting quantum yield for formation of t-BuC70- (Φ∞ = 0.45) is significantly larger than the value (Φ∞ = 0.21) of t-BuC60- produced when C70 is replaced by C60. When t-BuBNAH is replaced by 1-benzyl-1,4-dihydronicotinamide (BNAH) or the dimeric form [(BNA)2], the selective one-electron reduction of C70 to C70*- is attained through photoinduced electron transfer from BNAH or (BNA)2 to the triplet excited state of C70. The limiting quantum yields for formation of C70*- in the photoreduction of C70 by BNAH and (BNA)2 exceed unity; Φ∞ = 2.0 and 1.9, both of which are also larger than the corresponding values for formation of C60*- (Φ∞ = 1.3 and 0.80, respectively). The enhanced reactivity of C70 as compared to C60 is ascribed to a more localized unpaired electron and negative charge in C70*- due to loss of symmetry which facilitates the follow-up reaction in competition with the back electron transfer to the ground-state reactant pair. In the case of 4-isopropy 1-1-benzyl- 1,4-dihydronicotinamide (i-PrBNAH), the photochemical reaction with C70 yields not only C70*- but also the isopropylated anion (i-PrC70-).