We developed an enantioselective voltammetric sensor based on a carbon-paste electrode modified by enantiomorphic crystals of bromotriphenylmethane for the recognition and determination of tryptophan enantiomers. Enantiomorphic crystals of bromotriphenylmethane were obtained under the condition of Viedma ripening. The electrochemical and analytical characteristics of the sensor were studied. The proposed sensor was used to recognize and determine the enantiomers of L- and D-tryptophan in model solutions of pharmaceutical preparations and in human urine and blood plasma samples. The sensor is easy to manufacture and exhibits high reproducibility and stability. It was shown that, in using chemometric data processing, the presence of even slight differences between the voltammograms of enantiomers recorded using the proposed carbon-paste electrode is sufficient for their reliable recognition.