The results of a quantitative reading of the cyclic voltammetry behavior of the tryptophan (Trp) enantiomers deposited on an electrochemically activated glassy carbon electrode (GCE) are presented. A combined method for “reading” the analytical signals based on the modified Fourier transform and GPCA was applied. It allows a quantitative description of a derivative (dJ/dU) of the measured VAG. This combined method essentially increases the limits of conventional PCA and can be applied to a wide set of electrochemical data. This combined method allows the differentiation and quantitative description of signals governed by the different structures of L- and D-Trp(s) in aqueous solutions.