Recently, the development of fibrous membranes for pollutant filtration from air or water has been a topic of great interest. However, these filters’ high and rapid fouling has limited their use. In response, we have prepared photocatalytic active membranes that harness the synergic effect between graphene oxide (GO) and graphitic carbon nitride (g-C3N4). The resulting composite demonstrated the highest photocatalytic activity (kobs = 88 × 10−3 min−1). This g-C3N4@GO composite was then carefully deposited on/in an electrospun polyvinyl difluoride (PVDF) fibrous membrane. The reproducible results of the chemical bonding of the composite to the PVDF matrix were evident during photocatalytic experiments after ten Rhodamine B (Rh B) photocatalytic degradation cycles. Importantly, the fiber structure analysis post-reaction did not reveal any fiber cracks or void formation defects, indicating the excellent chemical stability of the PVDF fibrous matrix. This research offers a promising, sustainable, eco-friendly, and efficient solution for removing pollutants from different environments, inspiring further exploration and development in this field.