This manuscript describes the pervaporation study of benzene (Bz)/cyclohexane (Chx) mixture through four new semifluorinated poly(ether amide) (PEA) membranes. The polymers were prepared by phosphorylation polyamidation reaction of isophthalic acid (IA) and four structurally different semifluorinated diamine monomers (BTAPPI, BTAPPHI, BTAPPF, BTAPPPI). The synthesized polymers were characterized by elemental analyses, FT-IR. (1)H and (13)C NMR, TGA, DSC, DMA, WAXD and Rheology study. The polymers showed very good thermal stability associated with high glass transition temperatures (230-290 degrees C), good mechanical strength and preferential solubility in organic solvents. The membranes of these polymers showed higher permeation flux with comparable pervaporation selectivity in comparison to many other polymers reported earlier. An attempt has been taken to draw a structure property correlation of the chemical structures of the polymers with their pervaporation performance. (C) 2010 Elsevier B.V. All rights reserved.