High surface area, highly sorbent, polyimide powders designed to replace or complement Tenax G-C were obtained in high yield from pyromellitic dianhydride (PMDA) and 4,4'-diaminodiphenylsulfone (DADS), by precipitation polymerization in tetrahydrofuran (THF) solvent. The intermediate polyamide-acid powders were cyclodehydrated to high BET surface area (25-50 sq. m./g) polyimide powders by slowly heating to 230-240 C in an evacuated rotary evaporator. About 40 weight percent of the powder was in the 200-500 micromoles particle diameter range desired for sorption sampling of vapor-phase organics. The polyimide powders are obtained as 0.01-1.0 micromoles diameter, loosely agglomerated, platelets and rod-like particles. Preliminary evaluation of the powder sorption/desorption characteristics with benzene vapor shows them to have greater capacity than Tenax but to have less desirable breakthrough characteristics due to slower sorption kinetics ascribed to inadequate connecting pore volume. However desorption occurs smoothly and quantitatively at 100 C.