Freshwater shortage is becoming one of the most critical global challenges owing to severe water pollution caused by micropollutants and volatile organic compounds (VOCs). However, current purification technology shows slow adsorption of micropollutants and requires an energy-intensive process for VOCs removal from water. In this study, a highly efficient molecularly engineered covalent triazine framework (CTF) for rapid adsorption of micropollutants and VOC-intercepting performance using solar distillation is reported. Supramolecular design and mild oxidation of CTFs (CTF-OXs) enable hydrophilic internal channels and improve molecular sieving of micropollutants. CTF-OX shows rapid removal efficiency of micropollutants (>99.9% in 10 s) and can be regenerated several times without performance loss. Uptake rates of selected micropollutants are high, with initial pollutant uptake rates of 21.9 g mg(-1) min(-1), which are the highest rates recorded for bisphenol A (BPA) adsorption. Additionally, photothermal composite membrane fabrication using CTF-OX exhibits high VOC rejection rate (up to 98%) under 1 sun irradiation (1 kW m(-2)). A prototype of synergistic purification system composed of adsorption and solar-driven membrane can efficiently remove over 99.9% of mixed phenol derivatives. This study provides an effective strategy for rapid removal of micropollutants and high VOC rejection via solar-driven evaporation process.