Electron donor-acceptor (EDA) complex photochemistry has become a burgeoning topic in the synthetic radical chemistry mediated by visible light; however, the theoretical insights into the reaction mechanisms are limited. Herein, accurate electronic structure calculations at the CASPT2//CASSCF/PCM level of theory were performed to investigate the paradigm example of EDA complex-enabled photoreaction for visible-light-driven dearomative perfluoroalkylation of β-naphthol. The excitation energy levels of the EDA complex are controlled by noncovalent interactions because the photoinduced intermolecular charge is enhanced when the noncovalent interaction becomes weaker, leading to the broad spectra ranging from UVA (<380 nm) to visible light (>500 nm). The competitiveness of the radical-radical coupling over the radical chain pathway is also regulated due to the tunable radical concentrations varying the excitation wavelength.