Photoelectro-Fenton (PEF) was carried out for concurrent removals of inorganic and organic pollutants with simultaneous applications of two different anodes (iron and copper). Cadmium and Direct Orange 26 (DO26) were selected as samples of the contaminants of textile wastewater and influential parameters (pH, current density, H2O2 dosage and electrolysis time) of PEF were evaluated on Cd and DO26 removals. Both mechanisms of coagulation and oxidation affected the removal of both pollutants. Optimal conditions were achieved with pH = 4.0, current density of 5 mA/cm2, 3 mM H2O2 and 40 min electrolysis time, and under these conditions, the dye was completely removed and the Cd removal efficiency was about 80%. Unlike H2O2, persulfate had no scavenging effect in high dosages. The effects of different anions and two matrixes (tap water and wastewater) on Cd and dye removals were investigated. The results showed that decolorization was reduced by the phosphate and nitrate ions while chloride ion accelerated the decolorization rate. In terms of Cd removal, no significant change was observed in the presence of the anions except for phosphate ion. The sludge of PEF was assessed by Fourier transform infrared, field emission scanning electron microscope and energy-dispersive X-ray spectroscopy.