Pervaporation is an energy-efficient technique for dehydrating organic solvents from aqueous mixtures. To develop a highly selective pervaporation membrane with broad usage, we incorporated three types of CuO particles (solid CuO-S, sea urchin-like CuO-U, and porous CuO-P) into sodium alginate (Alg) for fabricating the Alg/CuO mixed matrix membranes (MMMs). The CuO syntheses and membrane preparation are simple and eco-friendly. The synthesized particles and membranes were systematically characterized. The improved hydrophilic feature of Alg/CuO MMMs was validated from the reduced water contact angle and higher water swelling ratio with increasing CuO wt%. When the Alg/CuO MMMs were applied to the pervaporation of 30 wt% water/isopropanol (IPA) at 25 ℃, both the permeation flux and separation factor were enhanced significantly compared to the pure Alg membrane. The separation efficiency followed the order of Alg/CuO-S MMMs < Alg/CuO-U MMMs < Alg/CuO-P MMMs, in good agreement with their water swelling tendency. The incorporation of 3 wt% porous CuO-P particles in MMM achieved the optimal dehydration efficacy (normalized total flux of 3.5 kg m-2h−1, separation factor of ca. 5000, and water purity of 99.96 wt%, with a stable performance over 168 h). A further larger loading wt% led to a decreased separation selectivity due to more void formation from particle aggregation. With an increase in feed temperature, both the permeation flux and separation factor were improved; however, the increase in feed water concentration deteriorated the separation selectivity while enhancing the flux. Furthermore, the high selectivity and broad applicability of Alg/3% CuO-P MMM were fruitfully demonstrated by exhibiting superior separation efficiencies in dehydrating various polar aprotic solvents compared with several membranes discussed in the literature.