By means of transient UV-visible absorption spectra/fluorescence spectra, combined with electronic structure calculations, the present work focuses on characterizing the photophysical and electronic properties of five PCBM-like C(60) derivatives (F1, F2, F3, F4, and F5) and understanding how these properties are expected to affect the photovoltaic performance of polymer solar cells (PSCs) with those molecules as acceptors. Spectral data reveal that the fluorescence quantum yields (Φ(F)) are enhanced and the triplet quantum yields (Φ(T)) are lowered for the five PCBM-like C(60) derivatives as compared to those of the pristine C(60), suggesting that functionalization of a C═C double bond perturbs the fullerene's π-system and breaks the I(h) symmetry of pristine C(60), which results in modifications of photophysical properties of the fullerene derivatives. PBEPBE/6-311G(d,p)//PBEPBE/6-31G(d) level of electronic structure calculations yields the HOMO-LUMO gaps and LUMO energies, showing that the electron-withdrawing effect induced by the side chain functional groups perturbs LUMO energies, from which different open circuit voltages V(oc) are resulted. The predicted V(oc) from our calculation agrees with previous experiment results. Basically, we found that functionalization of a C═C double bond sustains the fullerene structure and its electron affinitive properties. Adducted side chains contribute to adjust the HOMO-LUMO gap and LUMO levels of the acceptors to improve open circuit voltage. The results could provide fundamental insights for understanding how structural modifications influence the photovoltaic performance, which paves a way for guiding the synthesis of new fullerene derivatives with improved performance in polymer solar cells.