In this review, we examined the interactions of metal complexes and metal surfaces with fullerenes. That information has been related to the formation of redox-active materials produced by electrochemical reduction of solutions of various transition metal complexes and, fullerene or fullerene adducts. These redox-active polymers are strongly bound to electrode surfaces and display electrochemical activity in solutions containing only supporting electrolyte. Extensive studies of the electrochemical behavior of these films have been used to characterize their properties and structure. The process that produces these poly-PdnC60 and poly-PtnC60 films can also produce composite materials that consist of metal nanoparticles interspersed with the poly-PdnC60 and poly-PtnC60 materials. The relationship between these redox-active films and conducting metal organic framework materials has been examined. These insoluble, redox-active polymers have potential utility for the adsorption of various gases, for the construction of capacitors, for sensing, for the preparation of metal-containing heterofullerenes, and for catalysis.