Well-distributed ruthenium (Ru) nanoparticles decorated on porous carbon nanofibers (CNFs) were synthesized using an electrospinning method and a reduction method for use in high-performance elctrochemical capacitors. The formation mechanisms including structural, morphological, and chemical bonding properties are demonstrated by means of field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). To investigate the optimum amount of the Ru nanoparticles decorated on the porous CNFs, we controlled three different weight ratios (0 wt%, 20 wt%, and 40 wt%) of the Ru nanoparticles on the porous CNFs. For the case of 20 wt% Ru nanoparticles decorated on the porous CNFs, TEM results indicate that the Ru nanoparticles with ~2-4 nm size are uniformly distributed on the porous CNFs. In addition, 40 wt% Ru nanoparticles decorated on the porous CNFs exhibit agglomerated Ru nanoparticles, which causes low performance of electrodes in electrochemical capacitors. Thus, proper distribution of 20 wt% Ru nanoparticles decorated on the porous CNFs presents superior specific capacitance (~280.5 F/g at 10 mV/s) as compared to the 40 wt% Ru nanoparticles decorated on the porous CNFs and the only porous CNFs. This enhancement can be attributed to the synergistic effects of well-distributed Ru nanoparticles and porous CNF supports having high surface area.