Organic pollutants and microorganisms have become the main challenge in sewage treatment for decades. This mainly results from rapidly developing industry and urbanisation. However, simultaneous clearance of the organic pollutants and microorganisms in water still remains challenging in wastewater treatment. To address this problem, a novel molecularly imprinted metal–organic framework (MOF)/polyacrylonitrile (PAN) hybrid nanofibrous membrane (MOF/PAN-MIM) was prepared for selectively adsorbing bisphenol A (BPA) and inhibiting bacterial fouling in water treatment. Based on the experimental results, the MOF/PAN-MIM showed higher affinity towards BPA as compared to any other organic pollutants and a selective adsorption order of BPA > bisphenol F (BPF) > bisphenol S (BPS) > phenol > nitrophenol > resorcinol with adsorption performance 56.63 mg·g−1. The kinetics and isotherm models of the adsorption of MOF/PAN-MIM towards BPA are best fitted to a pseudo-second-order mode and a Langmuir isotherm. The cyclic reusability of the membranes was demonstrated by the regeneration experiments, with a removal efficiency of 77.73% towards BPA and a negligible Cu ion leakage of 0.64% after six adsorption–desorption cycles. Additionally, the inhibition rate against E. coli and S. aureus was measured to be greater than 90% via the antibacterial assay. The above results indicated that the as-prepared MOF/PAN hybrid nanofibrous membrane has efficient selectivity, sustained cyclic adsorption ability, and antibacterial fouling effect, which can be used as a potential multi-functional filtration membrane in real wastewater treatment.