Abstract: The influence of temperature on encapsulation of various guest mercaptans in β-cyclodextrin(β-CD) was investigated by the competitive UV-Vis spectrophotometric method. The results indicated that β-CD could include different mercaptans to form inclusion compounds at different temperatures. The inclusion stability constants of β-CD including 1-butanethiol at 25.0, 30.0, 35.0, 40.0 and 50.0℃, were 49.37, 66.39, 93.88, 124.5, and 197.61 L/mol, respectively, and those of β-CD wrapping 2-methyl-1-propanethiol were 326.0, 364.6, 415.3, 472.2, and 592.4 L/mol, respectively. The thermodynamic parameters ΔG, ΔH, and ΔS of the inclusion process were -9.661 kJ/mol, 35.85 kJ/mol, and 152.63 J/(mol·K) for 1-butanethiol, and -14.34 kJ/mol, 19.35 kJ/mol, and 112.98 J/(mol·K) for 2-methyl-1-propanethiol, respectively. It was found that the inclusion abilities of β-CD encapsulating various mercaptans were all enhanced with the increase of temperature; β-CD could spontaneously include various mercaptans in the temperature range studied, and the inclusion process was endothermic and controlled by entropy. The outer water shell of the hydrophobic alkyl of the mercaptan was destroged, causing the increase of the number of free molecules and the increase of the degree of freedom for the hydrophobic alkyl of the mercaptan inserted into the cavity β-CD, which contributed to the increase of entropy.