AbstractThe vibrational corrections and the temperature dependence of the specific rotation of six rigid organic molecules (α‐pinene, β‐pinene, cis‐pinane, camphene, camphor, and fenchone) were calculated at three wavelengths using hybrid time‐dependent density functional theory (TDDFT). A technique for calculating the temperature dependence of the vibrational average of a molecular property has been applied to obtain the specific rotation of the molecules as a function of temperature. For cases in which accurate equilibrium optical rotations can be obtained as a “base value,” and for which there is little effect from solvation, accurate predictions of the trends in the temperature‐dependence of the specific rotations can be calculated. For other cases, the method can be used to extract purely vibrational contributions to the overall temperature dependence of optical rotation.