The solubility of icariin in acetone, acetoacetate, chloroform, and light petroleum in the 283.2‐318.2 K range was measured by ultraviolet-visible spectrophotometry. As the temperature increased, the solubility of icariin in the 4 solvents gradually increased. The solubility data correlated with the modified Apelblat equation. The dissolution enthalpy and entropy of icariin were determined using van’t Hoff plots. The dissolution enthalpy and entropy of icariin in the 4 solvents increases as acetone >acetoacetate >chloroform >light petroleum, which can be explained by the difference of the polarity indices between them. The polarity indices of the solvents affect the solubility behavior.