Herein, 1D titanium oxynitride nanowires (TiON NWs) with different morphologies are fabricated through the step-controlled heat treatments of electrospun nanowires, and their electrochemical performances are analyzed with regard to the physicochemical characteristics changed by post-annealing processes. The direct-nitridation (1step) and sequential oxidation-nitridation (2step) procedures are performed to convert as-prepared nanowires, consisting of titanium precursor and polymer, to TiON NWs (TiON-1step NW and TiON-2step NW). The TiON-1step NW exhibits relatively high surface area and pore volume, which can be attributed to small crystallite size and amorphous carbon species formed during the direct-nitridation step, whereas grain growth and carbon decomposition are observed in the TiON-2step NW. When the prepared nanowires are applied to electrochemical capacitors and oxygen reduction reactions (ORRs), the TiON-1step NW shows significantly higher performances than the TiON-2step NW (200% higher capacitance and 0.17 V lower half-wave potential in ORR). It is expected that the variation of electrochemical properties is mainly affected by morphological differences of the two TiON NWs. Residual carbon components in the TiON-1step NW also contribute to improved electrical conductivity as well as structural stability in the applied electrochemical reactions. More detailed analyses are performed to clearly elucidate the experimental results from the perspective of morphology modification.