Microporous polymers with rigid organic architecture offer a wide range of efficient on board hydrogen storage at low temperature. The fluoropolymers with intrinsic microporosity (MP1 and MP2) were synthesized and characterized. Characterization technique such as high resolution transmission electron microscopy (HRTEM) revealed that the highly stable microporous structure of MP2 was composed of nanoporous frame work which was further supported by the computational study. The high surface area and microporosity of the polymers were estimated by measuring the N-2 gas adsorption. The MP1 and MP2 exhibit BET surface areas 666 and 1050 m(2)/g respectively. The micropore size distribution curves show a higher concentration of subnanometer pores. The hydrogen storage capacity of the prepared polymers are promising and the performance relative to other microporous polymers is comparable. (C) 2008 Wiley Periodicals, Inc.