The article highlights the synthesis of two different fullerene core star-like dyad materials: fullerene-phenylene-alt-thiophene (FPTP) and fullerene-acetylene terminated phenylene-alt-thiophene (FAPTP). PTP was prepared by Suzuki cross coupling reaction, whereas, the APTP was synthesized by Suzuki-Sonogashira cross coupling reaction. Synthesis of FAPTP dyad is a unique example of extension of Suzuki-Sonogashira cross coupling reaction where bromo-fullerene behaves as an aryl halide and APTP acts as an acetylene terminated conjugated system. Number of addends attached to fullerene core was estimated by using thermal methods (TGA & DSC). Both the optical (2.57-2.59 eV) and electrochemical band gaps (1.91-2.29 eV) indicate lower values for dyads compared to polymers. Low HOMO values (- 5.79 to - 5.86 eV) and nearly overlapping cyclic voltammograms at different scan rates suggest good air and electrochemical stability for both polymers and dyads materials. Photovoltaic properties and energy level diagram reveal its electron-hole (carrier) transport mechanism and potential for solar cells application.