A key feature of prominent transition metal-containing photoredox catalysts (PCs) is high quantum yield access to long-lived excited states characterized by a change in spin multiplicity. For organic PCs, challenges emerge for promoting excited-state intersystem crossing (ISC), particularly when potent excited-state reductants are desired. Herein, we report a design exploiting orthogonal pi-systems and an intermediate-energy charge-transfer excited state to maximize ISC yields (Phi(ISC)) in a highly reducing (E-0* =-1.7 V vs SCE), visible-light-absorbing phenoxazine-based PC. Simple substitution of N-phenyl for N-naphthyl is shown to dramatically increase Phi(ISC) from 0.11 to 0.91 without altering catalytically important properties, such as E-0*.