The objective of this study was to verify experimentally the recovery of high-purity ethylene from LDPE off-gas by a vacuum swing adsorption process. Adsorbent for this purpose was prepared by the impregnation of AgNO3 on Montmorillonite clay. The prepared adsorbent with an original substrate-shaped form shows high adsorption selectivities of light olefins to the corresponding paraffins. A 4-bed vacuum swing adsorption process using the above adsorbent, in which steps comprise adsorption (feeding), cocurrent rinse with ethylene product, countercurrent desorption (production) of ethylene by vacuum pump, pressurization-1 with paraffin stream, pressurization-2 with the rinse off-gas from the other bed and pressurization-3 with paraffin stream, was experimentally applied to recover ethylene from LDPE off-gas. Ethylene product purity of 99.95% could be obtained with the recovery of over 93%. The ethylene productivity of prepared adsorbent was 1.98 mol/kg·hr.