All conjugated C-60-containing block copolymers (BCPs) based on quasi-living Grignard metathesis (GRIM) polymerization have been designed and synthesized for application in polymer solar cells (PSCs). The C-60-containing BCP can induce the formation of a self-organization nanostructure of P3HT domain. Moreover, this C-60-containing BCP serves as a compatibilizer to reduce the interfacial tension between the P3HT and C-60, thus help establishing a moderate phase-separated morphology with crystalline P3HT and C-60 domain. The performance up to 2.56%(AM 1.5G irradiation (100 mW/cm(2))) of a P3HT:C60 device can be achieved by using C-60-BCP as additive without any post-treatment.