Aminoglycoside antibiotics (AGs) in environmental water are emerging pollutants that must be removed to protect human health and the ecosystem. However, removing AGs from environmental water remains a technical challenge due to high polarity, stronger hydrophilicity and unique characteristics of polycation. Herein, a thermal-crosslinked polyvinyl alcohol electrospun nanofiber membrane (T-PVA NFsM) is synthesized and firstly leveraged as the adsorptive removal of AGs from environmental water. The thermal crosslinking strategy is demonstrated to enhance both the water resistance and hydrophilicity of T-PVA NFsM, thereby effectively interacting with AGs with high stability. Experimental characterizations and analog calculations indicate that T-PVA NFsM utilizes multiple adsorption mechanisms, including electrostatic and hydrogen bonding interactions with AGs. As a result, the material achieves 91.09%-100% adsorption efficiencies and a maximum adsorption capacity of 110.35 mg g-1 in less than 30 min. Furthermore, the adsorption kinetics follow the pseudo-second-order model. After eight consecutive adsorption-desorption cycles, T-PVA NFsM with a simplified recycling process maintains a sustainable adsorption capability. Compared with other forms of adsorption materials, T-PVA NFsM has significant advantages such as less consumption of adsorbent, high adsorption efficiency and fast removal speed. Therefore, T-PVA NFsM-based adsorptive removal holds promise for eliminating AGs from environmental water.