A process for the preparation of substantially pure dexmethylphenidate hydrochloride comprises formation of salt of methylphenidate with dibenzoyl-D-tartaric acid in a mixture of organic Sonbems selecred from the group comprising of halogenated aliphatic hydrocarbon and alkane nitrile to get a dibenzoyl-D-tartaric acid salt of methylphenidate and converting dibenzoyl-D-tartaric acid salt of methylphenidate into substantially pure dexmethylphenidate hydrochloride.