Optical rotations of a diverse set of chiral molecules have been calculated ab initio. In a majority of the molecules considered, the signs of the calculated optical rotations are in agreement with those of the corresponding experimental observations, and the magnitudes are in reasonable agreement. It is thus suggested that the ab initio optical rotations provide a convenient alternative approach Ca determine the absolute stereochemistry of chiral molecules. A group of molecules has also been identified where the sign of optical rotation predicted for a given configuration is at variance with the literature assignments, and further investigations are needed.