Soluble, high molecular weight linear fullerene polymers were synthesized by the Cu(I)-catalyzed azide-alkyne cycloaddition polymerization between dialkyne-substituted C-60 and diazide-substituted 1,3,5-tridodecyloxybenzene monomers. It was found that the alkylene spacer length significantly affects the solubility of the resulting polymers. After the optimization of the monomer structures as well as the purification by reprecipitation, soluble fullerene polymers with the number-average molecular weight (M-n) and polydispersity index (M-w/M-n) of 130,000 and 2.42, respectively, were produced. The fullerene polymers were soluble in common organic solvents, such as THF, CH2Cl2, CHCl3, and toluene. We found that fullerene polymer microfibers could be obtained by electrospinning of a CHCl3 solution at a certain polymer concentration.