Membrane technology provides a new choice to solve the looming clean water scarcity crisis. However, severe membrane fouling is a great challenge in the membrane-based water treatment field. In this study, a new hierarchical TiO2/V2O5 multifunctional membrane was fabricated for the first time by assembling TiO2/V2O5 composites as a functional layer on top of the polymer supporting layer. Compared with conventional membranes, this multifunctional membrane is capable of concurrently filtering water and removing water pollutants to produce clean water without membrane fouling. Hence, this membrane can sustain high permeate flux for a longer period. These virtues can be attributed to the following reasons, among others: 1) low resistance of the nanofibrous functional layer, 2) enhanced light absorption and scattering of the hierarchical nanostructure, and 3) facilitated charge separation owing to the heterojunctions between TiO2 and V2O5. This novel membrane opens up a new avenue for the fabrication of a next-generation multifunctional membrane.