In this work, the photocatalytic removal of reactive blue 19 (RB19) dye was investigated by employing ZnO-Ce nanoparticles decorated with biochar under LED irradiation. Synthesis of ZnO-Ce nanoparticles decorated with biochar was performed utilizing the co-precipitation procedure, and the texture and morphologyof the fabricated nanocomposite were analyzed using EDX, FESEM, XRD, TEM, BET, and FTIR techniques. Moreover, FESEM images demonstrated that ZnO-Ce nanoparticles were successfully decoratedon the surface of biochar. The specific surface areas of biochar and biochar@ZnO-Ce were 34.518 and 636.52 m2/g, respectively. To achieve the maximum yield in the removal of RB19 dye, the influence of operating variables including dye concentration, LED lamp power, biochar@ZnO-Ce catalyst dose, pH, and H2O2dose were explored. Besides, the maximum percentage of RB19 dye removal was 96.47% under optimal conditions, i.e. catalyst dosage of 100 mg, H2O2 dosage of 1 mL, pH of 9, initial dye concentration of 5 ppm, LED power of 50 W, and reaction time of 140 min. Also, the kinetic information revealed that the removal of RB19 dye was in accordance with the pseudo-first order kinetic model, and the reaction rate constant and correlation coefficient were determined to be 0.045 min− 1 and R2 = 0.990, respectively. Also, the recyclability of biochar@ZnO-Ce nanocatalysts was promising over five runs, and only 6.08% of RB19 dye removal efficiency decreased. Therefore, it can be concluded that the biochar@ZnO-Ce photocatalyst can be promisingly applied for the removal of azo dyes in the aqueous solutions.