In this work, a simple strategy for the synthesis of hetero‐nanostructured Ni/α‐Mn2O3 via surfactant‐aided co‐reduction method is reported. The as synthesized Ni/α‐Mn2O3 is applied as catalytic material for the aqueous phase reduction of 4‐nitrophenol (4‐NP) and organic dye pollutants, namely Rhodamine B (RhB), Methylene blue (MB), Rose Bengal (RB), Congo red (CR), and Methyl orange (MO) in the presence of a mild reducing agent, NaBH4. This synthetic route provides homogeneous dispersion of Ni nanoparticles over α‐Mn2O3 surface. The nanoparticles and support are characterized using XRD, SEM/EDX, TEM, AAS and BET surface area analyses. The Ni particles are spherical, crystalline and size ranges < 5 nm. Further, hetero‐nanostructured Ni/α‐Mn2O3 is established as a highly efficient recyclable catalyst for the reduction of 4‐NP to 4‐aminophenol (4‐AP). The HPLC and FTIR analysis shows that 4‐AP is the sole product of the reduction of 4‐NP. The Ni/α‐Mn2O3 also exhibits high activity towards reduction of cationic and anionic dye pollutants. Thus, the as synthesized hetero‐nanostructured Ni/α‐Mn2O3 can be considered as the future contender for the wastewater treatment.