Organic dyads with intramolecular charge-transfer (ICT) character are emerging as viable and more sustainable photocatalysts than metal-based complexes. Herein, a carbazole- and naphthalimide-based organic dyad (Cz-NI) was designed as an efficient organic photocatalyst for the direct C(sp3)-H carbamoylation of saturated aza-heterocycles. Aiming at understanding the effect of environment, especially the solvent polarity on photocatalysis performance, the excited-state dynamics of Cz-NI in different polar solvents were studied by femtosecond (fs) and nanosecond (ns) time-resolved transient absorption (TA) spectroscopy. Fs-TA measurements indicate that the formation of an intramolecular charge separation (ICS) state with twisted structural feature in polar solvents is driven and stabilized by solvation dynamics. Combined with chemical calculations, we found that orbital decoupling, poor conjugation between Cz and NI groups due to intramolecular torsional motion and transition moments associated with ICT emission, limits excited-state deactivation through radiation and nonradiation transition to the ground state. In addition, the orthogonal π-system of the ICS state enables the efficient spin-orbit, charge-transfer intersystem crossing to a triplet state, which is localized on the NI group. Spectroscopic and computational results reveal the formation of an ICS state at an appropriate energy that enables the population of the triplet state with high quantum yield, and the localized triplet state has long lifetime and high reduction potential for subsequent reactions. Therefore, solvent-solute interaction, especially the solvation-coupled excited-state structural relaxation, is the main factor that the photocatalysis efficiency of Cz-NI has a significant polarity correlation.