Cobalt-doped cerium oxide (Co–CeO2) was synthesized and wrapped inside alginate (Alg) hydrogel beads (Alg/Co–CeO2). Further, copper nanoparticles (Cu) were grown on Alg/Co–CeO2 beads. Cu decorated Alg/Co–CeO2 composite beads (Cu@Alg/Co–CeO2) were tested as a catalyst for the solar-assisted photodegradation and NaBH4-assisted reduction of organic pollutants. Among different dyes, Cu@Alg/Co–CeO2 was found to be the best catalyst for the photodegradation of acridine orange (ArO) under solar light and efficient in reducing methyl orange (MO) with the aid of NaBH4. Cu@Alg/Co–CeO2 decolorized ArO up to 75% in 5 h under solar light, while 97% of MO was reduced in 11 min. The decolorization efficiency of Cu@Alg/Co–CeO2 was further optimized by varying different parameters. Thus, the designed catalyst provides a promising way for efficient oxidation and reduction of pollutants from industrial effluents.