This work is to study the variations of adsorption characteristics of binary vapor according to packing system of double-layer bed by fixed bed experiment. Breakthrough curves of single and binary vapor composed of acetone and benzene on single-layer and double-layer adsorption bed composed of activated carbon (AC) and silica-aluminar (SA) were compared. Adsorptions of binary vapor on double-layer bed were influenced by the differences of surface area between adsorbents as well as the polarity difference between adsorbent and adsorbate. The roll-up phenomenon of acetone vapor was happened by replacement with competing adsorption between acetone vapor and benzene vapor on AC bed, but it was not happened on SA bed because acetone vapor and benzene vapor had less difference in affinity with SA bed. The breakthrough times of acetone vapor and benzene vapor on AC/SA double-layer bed were three times and 1.4 times larger respectively than on SA/AC double-layer bed, the differences of breakthrough times were relatively larger than the equilibrium adsorption capacities according to packing system of double-layer bed.