A pyridine-functionalized pyrazolinofullerene (1) was synthesized in 42% yield via an improved one-pot reaction of C60, 3,6-di(2-pyridyl)-1,2,4,5-tetrazine, and water. The structure of 1 was unambiguously determined by X-ray diffraction of its single crystal. Due to the coordination capability of the functional groups on fullerene, compound 1 was used as a buffer layer to modify ZnO in inverted polymer solar cells. The power conversion efficiency was improved from 3.65% to 4.18% for inverted P3HT:PC61BM solar cells.