Polyester side-chain grafted poly(aryleneethynylene)s (PEPAE) containing benzene and thiadiazole units were synthesized. Electrospinning allowed processing these PEPAEs into nanostructured materials. Large surface areas could be uniformly covered (100 cm(2)) by this technique. Side chain length, polymer concentration and solvent determined the type of nanostructure (nanofibers or microspheres) formed. When a polyester substituted poly(p-phenyleneethynylene) was electrospun into liquid nitrogen, a unique type of nanoporous morphology emerged.