Many chiral selectors have been used for recognition of enantiomeric compounds but their synthesis involves time-consuming and expensive multistep-processes with almost not optically pure products. In this paper, 1-butyl-3-methylimidazolium (T-4)-bis[(αS)-α-(hydroxy-O) benzeneacetato-κO] borate, a chiral ionic liquid which can be easily synthesized, was first used as a chiral selector in solution. The enantiomer compositions of propranolol hydrochloride were determined by using this chiral selector and the spectrophotometric method. The data of UV spectra showed that S-propranolol hydrochloride could be recognized in the mixture of the enantiomers with a total concentration of 1.50 × 10−4 M.