As one kind of conducting polymer composite, poly(3,4-ethylenedioxythiophene): poly(styrenesulfonic acid) (PEDOT:PSS) has been widely used as an electrode for energy storage and conversion devices because of its optical transmittance, flexibility, and high electrical conductivity etc. Here, we prepared binding-free PEDOT:PSS fibers (PFs) electrodes with high capacitive performance for supercapacitors via a facile method followed by various solvent treatments. Dimethyl sulfoxide (DMSO)-treated electrodes displayed a better specific capacitance (C-s) of 202 F/g at 0.5 A/g with higher elongation at break, flexibility, and conductivity of 140.7 S/cm, compared to those of pristine PEDOT:PSS materials. More importantly, the DMSO-treated fibers possessed improved stability, which retained 105% of the initial C-s after 22 000 long cycles at 10 A/g. It is believed that the fabricated PFs will be promising organic electrodes for portable supercapacitors and other flexible electronic devices in the near future.