Ureido-functionalized mesoporous polyvinyl alcohol/silica composite nanofibre membranes were prepared by electrospinning technology and their application for removal of Pb2+ and Cu2+ from wastewater was discussed. The characteristics of the membranes were investigated by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and N2 adsorption-desorption analysis. Results show that the membranes have long ﬁbrous shapes and worm-like mesoporous micromorphologies. Fourier transform infrared spectroscopy confirmed the membranes were successfully functionalized with ureido groups. Pb2+ and Cu2+ adsorption behavior on the membranes followed a pseudo-second-order nonlinear kinetic model with approximately 30 minutes to equilibrium. Pb2+ adsorption was modelled using a Langmuir isotherm model with maximum adsorption capacity of 26.96 mg g−1. However, Cu2+ adsorption was well described by a Freundlich isotherm model with poor adsorption potential due to the tendency to form chelating complexes with several ureido groups. Notably, the membranes were easily regenerated through acid treatment, and maintained adsorption capacity of 91.87% after five regeneration cycles, showing potential for applications in controlling heavy metals-related pollution and metals reuse.