The composite membranes of acrylate polymers and porous substrate were prepared. The separation of the organic solvent-water mixtures and the organic solvent-organic solvent mixtures through these membranes by pervaporation was investigated. The acrylate copolymer membrane showed the organic solvent permselectivity for the separation of the organic solvent-water mixture, especially for the chlorinated hydrocarbon-water mixture separation. The high organic solvent permselectivity should be governed by solubility selectivity. The influence of the ester residue of acrylate on the phenol-water mixture separation was observed. The copolymerization of the macromonomers containing the polystyrene, poly(methyl methacrylate), and polydimethylsiloxane chain had a small effect on the separation of the chlorinated hydrocarbon-water mixture. High flux and low selectivity of organic solvent were observed in the case of the organic solvent mixture separation through the n-butylacrylate membrane. The difference of permeability of organic solvent was observed for the acrylate copolymer which has Various structures of ester residue.