Solar-driven desalination has emerged as a sustainable and efficient solution for addressing global water scarcity, especially beneficial in remote, off-grid, and disaster-affected regions. Among emerging technologies, photothermal membrane distillation (PMD) stands out due to its effective solar-energy conversion, scalability, and simplicity. Here, we report a hybrid PMD membrane fabricated by electrospinning MXene (Ti3C2Tx) nanosheets integrated with silver nanoparticles (AgNPs) onto a poly(vinylidene fluoride-co-hexafluoropropylene) (PH) substrate. The hybrid membrane synergistically combines MXene’s exceptional photothermal conversion capabilities and the broad-spectrum antibacterial properties of AgNPs, thereby achieving enhanced permeate flux, excellent salt rejection (>99.99%), and superior resistance to biofouling. Under simulated solar irradiation (1 sun), the fabricated PMD membranes demonstrated permeate fluxes of 0.94 LMH and 3.08 LMH at ambient temperature (∼20 °C) and 30 °C, respectively, achieving a remarkable photothermal efficiency of 63.5% at ambient temperature, with a 35 g/L NaCl feed solution. When challenged with real Red Sea water (39 g/L salinity), the permeate flux showed only a marginal reduction (8.5%), underscoring excellent antifouling performance under realistic conditions. Beyond its desalination performance, the membrane demonstrated excellent antibacterial properties with a 99.8% killing effect. These findings underscore the potential of the Ag@MXene/PHNF membrane as a robust, scalable, and sustainable solution for decentralized water production, capable of producing approximately 24 L of potable water per square meter per day.