While WCl6-Ph4Sn is a poor catalyst for the polymerization of 1-phenyl-1-butyne (PB) at room temperature, it effectively polymerizes PB in the presence of C-60, giving high molecular weight polymers in high yields. The polymers are soluble in common solvents such as THF and chloroform, and spectroscopic analysis reveals that C-60 has copolymerized with PB. Thus, C-60 plays the dual roles of comonomer and cocatalyst in the acetylene polymerization. While it has often been reported that C-60 quenches photoluminescence (PL) of conjugated copolymers, the C-60-containing polyacetylene emits strong blue light, whose intensity is about two times higher than that of the PL of the parent PPB.