During the initial cooling period of spent nuclear fuel, Cs-137 and Sr-90 constitute a large portion of the total decay heat. Therefore, separating cesium and strontium from spent nuclear fuel can significantly decrease decay heat and facilitate disposition. This study presents analytical technique based on the gas pressurized extraction chromatography (GPEC) system with cation exchange resin for the separation of Sr, Cs, and Ba. GPEC is a micro-scaled column chromatography system that allows for faster separation and reduction volume of elution solvent compared to conventional column chromatography by utilizing pressurized nitrogen gas. Here, we demonstrate the comparative study of the conventional column chromatography and the GPEC method. Cation exchange resin AG 50W-X12 (200~400 mesh size) was used. The sample was prepared at a 0.8 M hydrochloric acid solution and gradient elution was applied. In this case, we used the natural isotopes 88Sr, 133Cs, and 138Ba instead of radioactive isotopes for the preliminary test. Usually, cesium is difficult to measure with ICP-OES, because its wavelengths (455.531 nm and 459.320 nm) are less sensitive. So, we used ICP-MS to determine the identification and the recovery of eluate. In this study, optimized experimental conditions and analytical result including reproducibility of the recovery, total analysis time and volume of eluents will be discussed by comparing GPEC and conventional column chromatography.