In this research, the C50 fullerene was employed as the source of the π electrons and the electron donor-acceptor groups were used to enhance its optical properties. Considerable enhancement in its electronic and optical property of as the result of donor and acceptor group presence was observed. For instance, in UV-Visible absorption spectrum, the number of absorption lines significantly increase which may be the relaxation of the electronic transition selection rules. Considerably, the substituted forms of C50, has numbers of absorption bands in near infrared region. The BH2–C50-NCH3Li and NO–C50-NCH3Li molecules have superior improvement in optical properties. Finally, the donor and acceptor groups influence on non-linear optical properties (NLO) of C50 were explored and the considerable improvement in NLO properties of C50 was observed which the NLO improvements for BH2-C50-NCH3Li and NO-C50-CH2Li cases is higher than others.