Separation of radioisotope Kr-85 from Xe-136 is of importance in used nuclear fuel reprocessing. Membrane separation based on zeolite molecular sieves such as chabazite SAPO-34 is an attractive alternative to energy-intensive cryogenic distillation. We report the synthesis of SAPO-34 membranes with considerably enhanced performance via thickness reduction based upon control of a steam-assisted vapor solid conversion technique followed by ion exchange with alkali metal cations. The reduction of membrane thickness leads to a large increase in Kr permeance from 7.5 to 26.3 gas permeation units (GPU) with ideal Kr/Xe selectivities >20 at 298 K. Cation-exchanged membranes show large (>50%) increases in selectivity at ambient or slight subambient conditions. The adsorption, diffusion, and permeation characteristics of ion-exchanged SAPO-34 materials and membranes are investigated in detail, with potassium-exchanged SAPO-34 membranes showing particularly attractive performance. We then demonstrate the fabrication of selective SAPO-34 membranes on alpha-alumina hollow fibers.