Linear free energy relationship (LFER) parameters are routinely used to parametrize physicochemical effects while investigating reaction mechanisms. In this Communication, we describe an alternate application for LFERs: training sets for model building in an analytical application. In this study, the sterics, quantified by Charton parameters (Delta v), of nine secondary chiral alcohol analytes were correlated to the circular dichroism output from a chiral alcohol optical sensor. To test the validity of the model, the correlative linear model was applied to determine the enantiomeric excess of samples of two alcohols without a priori knowledge of a calibration curve. The error in this method was comparable to those of previous experimental methods (<5%).