Photocatalysis is useful for the long-term goal of a pollution-free environment. However, the development of new photoactive materials with enhanced photoconversion efficiency remains a serious bottleneck. This study demonstrates the preparation of low-cost, nontoxic, rod-like β-Mn2V2O7 using a simple, cost-effective fabrication method. The proposed photoactive material was characterized using several analytical techniques to determine its physiochemical properties, while its photocatalytic ability for the removal of organic pollutants under direct sunlight was also assessed. The prepared β-Mn2V2O7 was found to efficiently remove both Rhodamine B and methylene blue from an aqueous solution. The photoinduced and ultra-sound-assisted catalytic reduction of 4-nitrophenol (4-NP) was also demonstrated. The hydrogen-evolved photocatalytic removal of 4-NP was evaluated with different amounts of ethanol as a scavenger, with 10% ethanol exhibiting optimal efficiency. The superior organic pollutant removal ability of the proposed material is ascribed to its high surface area, superior optical properties, and suitable band edges.