A batch technique was applied to determine the equilibrium adsorption of benzene from its benzene/octane and benzene/octene mixture on NaX (Si:Al 1.20) and NaY (Si:Al 2.79) in liquid phase. Benzene was preferentially adsorbed from both mixtures on NaX and NaY. Regardless whether octane or octene was present in the binary mixture, benzene was adsorbed more selectively on the high-silica NaY compared to NaX, which contained more cations. The presence of cations on the SIII/SIII' site inside the supercages of NaX causes a more difficult hosting of benzene inside the supercages of NaX and especially on the 12-membered ring site. However, at sufficiently high external benzene concentration (>10 mol %), the 12-membered ring site of NaX will be occupied by benzene, leading to a maximum adsorption capacity of five benzenes per supercage on both NaX and NaY. The double bond present inside octene allows the molecules to compete for the adsorption sites with benzene. The competitive effect of octene prevents the fifth benzene molecule to adsorb in the NaX supercage within the investigated concentration range.