Composite and chemically/physically distinct fibers of sodium poly[2-(3-thienyl)-ethoxy-4-butylsulfonate] (PTEBS) and polyethylene oxide (PEO) were formed by electrospinning from a homogeneous aqueous solution containing PTEBS and PEO co-solutes. Composite nanofibers of diameter of similar to 60 nm were electrospun from an aqueous solution. The addition of ammonium hydroxide (NH4OH) to the water solution resulted in "bimodal" electrospun fibers consisting of distinct large diameter white PEO fiber segments and small diameter black PTEBS fiber segments. The optical absorption spectrum of the composite PTEBS/PEO nanofibers did not exhibit the characteristic peak around 460 nm, which is present in the bulk spectrum. (c) 2008 American Institute of Physics.