The feasibility study of the application of the photoelectrocatalytic and electrolytic/UV decolorization of Rhodamine B (RhB) was investigated in the photoelectrocatalytic and electrolytic/UV process with $TiO_2$ photoelectrode and DSA (dimensionally stable anode) electrode. Three types of $TiO_2$ photoelectrode were used. Thermal oxidation electrode (Th-$TiO_2$) was made by oxidation of titanium metal sheet; sol-gel electrode (5G-$TiO_2$) and powder electrode (P-$TiO_2$) were made by coating and then heating a layer of titania sol-gel and slurry $TiO_2$ on titanium sheet. DSA electrodes were Ti and Ru/Ti electrode. The relative performance for RhB decolorization of each of the photoelecoodes and DSA electrodes is: Ru/Ti > Ti > SG-$TiO_2$ > Th-$TiO_2$. It was observed that photoelectrocatalytic decolorization of RhB is similar to the sum of the photocatalytic and electrolytic decolorization. Therefore the synergetic effect was not showed in pthotoelectrocatalytic reaction. $Na_{2}SO_{4}$ and NaCl showed different decolorization effect between pthotoelectrocatalytic and electrolytic/UV reaction. In the presence of the NaCl, RhB decolorization of Ru/Ti DSA electrode was higher than that of the other photoelectrode and Ti electrode. Optimum current, NaCl dosage and UV lamp power of the electrolytic/UV process (using Ru/Ti electrode) were 0.75 A, 0.5 g/L and 16 W, respectively.