In practice, adsorbents such as 13X have strong hydrophilicity due to their low Si/Al ratio, whose competitive adsorption between vapour and volatile organic compounds (VOCs) often impairs the actual removal effect of VOCs on the adsorbents. Here, 13X was modified using CTABr as a templating agent and tetraethoxysilane (TEOS) as a silica source.Based on this modified 13X, a core-shell composites with 13X core and a mesoporous silica shell, named as 13X@SiO₂, was therefore synthesized. Its adsorption performance was tested by using toluene as a probe molecule under different humidity conditions on a penetration experimental device, compared with that of the pristine 13X. The results show that the adsorption capacity of sample 13X@SiO₂-2.6 (2.6 mL TEOS added in the preparation) was about 18% higher than that of 13X original sample under dry conditions. At 30% and 50% relative humidity, the optimum adsorption capacity of 13X@SiO₂ was increased by about 53% and 90%, respectively. In order to test the stability and reusability of the adsorbents, twice regeneration of sample 13X@SiO₂-2.6, treated for 2 h in situ desorption at 350 ℃, were performed, and the result showed that the regenerated sample 13X@SiO₂-2.6 still retained 90% of the original toluene adsorption capacity.