A new composite adsorbent SiO2·xH2O·yCaCl2 which is composed of macro-porous silica gel and calcium chloride is introduced. In order to analyze its adsorption theory, adsorption and desorption isotherms, BET surface areas, pore volumes and average pore diameters of macro-porous silica gel and four composite adsorbent samples with different CaCl2 content are measured using SEM and Asap2010 apparatus. From the adsorption isotherms, desorption isotherms and lag loops, it can be deduced that the main pore structure in macro-porous silica gel and the new composite adsorbent have two shapes: taper with one top open and taper or hyperbolic taper with both ends open. Based on the analysis of pore diameter distribution and lag loop, a sketch map showing calcium chloride filled in pore of macro-porous silica gel is presented. The adsorption isotherms at 25℃ are measured. Experimental results show that the new composite adsorbent can adsorb more water than common adsorbents (macro-porous silica gel, micro-porous silica gel and synthetic zeolite 13X). In the light of the results of pore structure, adsorption isotherms and lyolysis phenomenon are analyzed.