Silicas were prepared by a sol-gel method from tetraethoxysilane and acetic anhydride in the presence of cholesterol in organic solution media. Some silicas had higher pore volumes than silicas obtained in the absence of cholesterol. The adsorption abilities by these silicas were compared using various compounds in benzene solution. Although no clear difference among their adsorptions of cholesterol was observed, progesterone and other analogous steroid hormones were well adsorbed by silicas prepared in the presence of cholesterol, especially, prepared with n-heptane as an additional solvent. This silica adsorbed steroid hormones more selectively than other analogous compounds such as bisphenol A and hexestrol. On the other hand, a silica prepared by the usual aqueous sol-gel method with cholesterol had no clear adsorption selectivity to steroid hormones. Furthermore, no selective adsorption of steroid hormones was observed in the case of a common silica gel for column chromatography. This unique property of adsorption observed in silicas prepared using acetic anhydride in the presence of cholesterol is likely to be induced by the imprinting effect of the steroid skeleton part of cholesterol in silica matrix.