High performance polydimethylsiloxane (PDMS) membranes for n-butanol recovery were fabricated using a tri-functional crosslinker containing the phenyl group. In order to understand the role of the functional group structure and cross-linking density in pervaporation performance, PDMS membranes were prepared using tri-functional crosslinker containing other functional groups (hexyl and cyclohexyl) and conventional tetra-functional crosslinker. The relationship between the polymer structure-performance was discussed based on the sorption and diffusion properties of the membranes. As a result, the phenyl-based PDMS membrane exhibited the pervaporation performance owing to the strong hydrophobicity and chain rigidity of the phenyl group compared to other PDMS membranes even at high butanol concentration and high temperature conditions.