A novel photocatalyst based on the design of P-N heterojunction between hollow spherical Mn3O4 and nanorods shape of α-Ag2WO4 is synthesized using a sonication-deposition–precipitation route. The nanocomposite Mn3O4/α-Ag2WO4(60%) exhibits a great potential towards nitroarenes (including 4-nitrophenol, 4-nitro-aniline and 4-Nitro-acetanilide) reduction under visible light irradiation exceeding that of Mn3O4/α-Ag2WO4(40%) as well as their individual counterparts (3–5%). The Mn3O4/α-Ag2WO4(60%) catalyst exhibited an excellent photo-reduction activity comprised of 0.067 s−1 towards 4-nitrophenol (0.001 M) in only 60 s reaction time using NaBH4 (0.2 M). This was due to the successful formation of the Mn3O4/α-Ag2WO4 composite as validated by XRD, TEM-SAED, XPS, FTIR, UV–Vis diffuse reflectance and PL techniques. Decreasing the Eg value into 2.7 eV, the existence of a new (151) plane in the composite beside enhancement of the composite electrical conductivity (1.66 × 10–7 Ω−1 cm−1) helps the facile nitroarenes adsorption and hydrogenation. Transient photocurrent response and linear sweep voltammetry results prove the facilitation of photogenerated charge carriers separation and transport via improving electron lifetime and lessening recombination rate. The composite photocatalyst produced higher amounts of H2 production, when inserted in a typical reaction medium containing NaBH4, comprised of 470 µ mole/g exceeding those of the counterparts (35 µ mole/g). This photocatalyst is strikingly hydrogenated 4-nitrophenol under mild conditions (25 °C and 0.35 MPa pressure of H2) with magnificent rate constant equal 34.9 × 10−3 min−1 with 100% selectivity towards 4-aminophenol.