This study presents a new solar-driven hybrid system that integrated a photo-electrochemical reactor with a photovoltaics (PV) panel for azo dyes' decolorization and electricity generation. Full spectrum of sunlight is utilized to optimize the color removal of Acid Red 26 (AR26) in this hybrid system. Persulfate (PS, S2O42-) was selected as the photochemical oxidant and Ti/IrO2-Ta2O5 electrode was used as the anode. Experiments were made to evaluate the efficiency of decolorization and the performance of PV panels in different reaction conditions outdoors. The results showed that the synergistic effect of two processes was observed for the AR26 decolorization. Comparing with the solar/persulfate process or the electrochemical process alone, the complete color removal time by the hybrid system decreased up to 50% and 44.4% respectively. In this system, the water layer in the flow channel cooled PV panels by absorbing the far infrared spectrum of sunlight, and the increased temperature of wastewater from 7 degrees C to 16 degrees C enhanced the decolorization efficiency of AR26. Moreover, the generated electricity by PV panels could satisfy the energy demand of electrochemical oxidation.