<p>Pervaporation membrane technology offers distinct advantages over reverse osmosis for desalinating high-salinity water. However, achieving high water flux of membranes at low temperature remains a challenge. Here we report a solar–vacuum dual-driven desalination system using photo-responsive covalent organic framework membranes. By applying solar driving force at the nanochannel entrances, the photothermal and photoelectric effects are harnessed to disrupt the hydrogen bond networks and lower the energy barriers for water entry. Subsequently, water undergoes rapid transport through the functionalized nanochannels under vacuum driving force. The system achieves an exceptional water flux of 120 kg m⁻² h⁻¹ for high-salinity brine (7.5 wt%) at 30 °C with &gt;99% salt rejection—equivalent to the water flux of conventional pervaporation at 70 °C. Moreover, it demonstrates robust high performance (for example, 240 kg m⁻² h⁻¹ for seawater) across a wide salinity range (0.1–7.5 wt%), enabled by membranes’ structural stability, as well as its well-matched polarity and hydrophilicity. Our work offers new insights into mass–energy coupling for achieving high-efficiency low-temperature desalination and opening a promising pathway for the development of sustainable desalination technology.</p>