TiO2 multi-electrodes composed of nanoparticles and nanorods were prepared for use as electrodes in dye-sensitized solar cells (DSSC) in an effort to improve the light-to-electricity conversion efficiency. TiO2 nanorods have been successfully prepared via electrospinning methods using a solution containing titanium isopropoxide (TIP). Acetic acid is generally used as a catalyst in sol-gel processes involving TIP; however, acetic acid induces rapid solidification of the sol solution, resulting in clogging of the nozzle during electrospinning, thereby hindering the mass production of TiO2 nanorods. In this work, we introduced acetyl acetone as a new catalyst and optimized the electrospinning conditions of TiO2 nanofibers. The use of acetyl acetone catalysts dramatically extended the solidification time of the TIP sol solution. The DSSC efficiency was improved through the use of TiO2 multi-electrodes.