Fullerene materials have been widely used to fabricate efficient and stable perovskite solar cells (PSCs) due to their excellent electron transport ability, defect passivation effect, and beyond. Recent studies have shown that fullerene-related chemical interaction has played a crucial role in determining device performance. However, the corresponding fullerene-related chemical interactions are yet well understood. Herein, a comprehensive review of fullerene materials in regulating carrier transport, passivating the surface and grain boundary defects, and enhancing device stability is provided. Specifically, the influence of the fullerene-related chemical interactions, including fullerene-perovskite, fullerene-inorganic electron transport layer (IETL), and fullerene-fullerene, on the device performance is well discussed. Finally, we outline some perspectives for further design and application of fullerene materials to enhance the performance and commercial application of PSCs.