To develop flexible adsorbents for compact volatile organic compound (VOC) air purifiers, flexible as-spun zeolite fibers are prepared by an electrospinning method, and then zeolite particles are exposed as active sites for VOC (toluene) adsorption on the surface of the fibers by a thermal surface partial etching process. The breakthrough curves for the adsorption and temperature programmed desorption (TPD) curves of toluene over the flexible zeolite fibers is investigated as a function of the thermal etching temperature by gas chromatography (GC), and the adsorption/desorption characteristics improves with an increase in the thermal surface etching temperature. The effect of acidity on the flexible zeolite fibers for the removal of toluene is investigated as a function of the SiO2/Al2O3 ratios of zeolites. The acidity of the flexible zeolite fibers with different SiO2/Al2O3 ratios is measured by ammonia-temperature-programmed desorption (NH3-TPD), and the adsorption/desorption characteristics are investigated by GC. The results of the toluene adsorption/desorption experiments confirm that a higher SiO2/ Al2O3 ratio of the flexible zeolite fibers creates a better toluene adsorption/desorption performance.