In this study, an asymmetric membrane containing an electrospun copper benzene-1,3,5-tricarboxylate (Cu-BTC)/poly(vinyl alcohol) (PVA) pre-selective layer and a dense PVA separation layer (M-CuBTC) was fabricated. The existence of the electrospun Cu-BTC/PVA composite nanofibre layer coated on a dense PVA membrane was observed to significantly improve the separation performance and membrane permeability by serving as a hydrophilic pre-selective barrier during the application of the M-CuBTC membrane to the pervaporation dehydration of aqueous 1,4-dioxane solutions. The M-CuBTC membrane demonstrated improved pervaporation performance, with a total permeation flux of 87.69 g/m(2) h, a separation factor of up to 1852.32, a water permeance of 2102.87 gpu, and a water selectivity of 1365.96. It is interesting to note that due to the addition of the electrospun pre-selective layer, the permeation flux demonstrated by the MCuBTC membrane was double of that of the dense PVA membrane, while the separation factor increased from 392.65 to 1852.32.