Polymers with bulky substituents are of pronounced interest in membrane based separation applications. In this direction, the present work reports the synthesis and characterization of a series pendant di-tert-butyl and trifluorometyl groups containing new poly(ether imide)s (PEIs). The PEIs were prepared by thermal imidization of polyamic acid which is derived by the reaction of a diamine monomer, namely 1,4-bis-[{2'-trifluoromethyl 4'-(4 ''-aminophenyl)phenoxy}] 2,5-di-t-butylbenzene (FMTBDA) with four different commercially available aromatic dianhydrides, i.e. BPADA, 6FDA, ODPA, and BTDA. The PEIs are soluble in many organic solvents and show reasonably high intrinsic viscosity (0.87 to 1.10 dL/g in NMP) and weight average molecular mass as high as 371,900 g/mol with a polydispersity index of 3.8. The proton NMR and FTIR spectroscopic investigation are in accordance with the respective polymer repeating unit structures. The physical properties of the polymers like thermal and mechanical stability are investigated thoroughly to assess their suitability for membrane based application. The polymers are thermally stable up to 474 degrees C with 10% weight loss temperature in air environment and have a glass transition temperature as high as 253 degrees C. The polymer membranes have satisfactory mechanical strength with stress at break value up to 95 MPa. The gas permeability coefficients of the PEIs are somewhat higher than those of other polyimides prepared from the same dianhydrides.