This study has carried out to evaluate the effect of NaCI as electrolyte of single (electrolysis and UV process) and complex (electrolysis/UV) processes for the purpose of removal and mineralization of Rhodamine B (RhB) dye in water. It also evaluated the synergetic effect on the combination of electrolysis and UV process. The experimental results showed that RhB removal of UV process was decreased with increase of NaCl, while RhB removal of electrolysis and electrolysis/UV process was increased with increase of NaCI. The decolorization rate of the RhB solution in every process was more rapid than the mineralization rate identified by COD removal. The latter took longer time for further oxidation. Absorption spectra of an aqueous solution containing RhB showed a continued diminution of the RhB concentration in the bulk solution: concomitantly, no new absorption peaks appeared. This confirmed the decolorization of RhB, i.e., the breakup of the chromophores. It was observed that RhB removal in electrolysis/UV process is similar to the sum of the UV and electrolysis. However, it was found that the COD of RhB could be degraded more efficiently by the electrolysis/UV process than the sum of the two individual process. A synergetic effect was demonstrated in electrolysis/UV process.