Polyethylene glycol monomethyl ether (mPEG)-co-polyaniline (PANI) is presented and the effect of this low molecular weight copolymer on properties of electrospun fibers obtained from its blends with polycaprolactone (PCL) was investigated. MPEG-co-PANI was synthesized by esterification of mPEG with 4-amino benzoic acid and polymerization of aniline from amine-capped mPEG. Molecular weight of polyaniline segment was determined by H-1 NMR spectroscopy. Electroactivity of blend was confirmed by cyclic voltammetry. Field Emission Microscope showed that presence of low molecular weight copolymer with PANI segment resulted in fibers without any beads and average size of micrometer. This novel system offers new possibilities in biomedical applications.