The wide presence of pharmaceuticals and personal care products (PPCPs) in water is a major concern regarding current emerging pollution and urges their selective monitoring to establish water quality management. Microporous materials have been developed to extract organic contaminants and further embedded as fillers into polymeric composites like matrix-mixed membranes (MMMs) for practical use. Considering the relatively large molecular size of PPCPs and their slow diffusion in the membrane, the MMM configuration is, however, inadequate for liquid-phase separations. Here we report pore-networked membranes (PNMs) based on the concept of interconnecting the microporous fillers within the polymer matrix to form a continuous porous phase. Linked metal-organic polyhedra (MOP) network is designed for the continuous porous phase with tunable micro/mesopores, which are accessible for big PPCP molecules to facilitate their diffusion and adsorption. By contrast to MMMs, PNMs show enhanced stability, capacity and extraction selectivity towards specific pharmaceutical drugs amongst 13 PPCPs in environmental water matrices at trace-level concentrations.