In this work we have fabricated P84 asymmetrical flat sheet membranes with a sponge-like structure by carefully formulating the polymer dope, followed by crosslinking the P84 membranes with a tripodal amine (tris(2-aminoethyl)amine (TAEA)) in a methanol solution, combined with heat treatment. The separation performances for acetone dehydration as functions of dope formulation, TAEA crosslinking time and post annealing duration were further investigated and optimized by using the Taguchi statistical method. The membrane with the best pervaporation performance possessed a high separation factor of 983 with a reasonable flux of 0.658 kg m(-2) h(-1). FESEM, FTIR and XPS were employed to elucidate the crosslinking mechanisms and explain the evolution of physicochemical properties and chemistry-performance relationship. A benchmark comparison indicates that the newly developed P84/TAEA crosslinked membrane has good separation performance for acetone dehydration. (C) 2014 Elsevier Ltd. All rights reserved.