Using the net analyte signal, hybrid linear analysis was proposed to predict chemical concentration. In this paper, we select a sample from training set and apply orthogonal signal correction to obtain an improved pseudo unit spectrum for hybrid least analysis. using the mean spectrum of a calibration training set, we first show the calibration by hybrid least analysis is effective to the prediction of not only chemical concentrations but also physical property variables. Then, a pseudo unit spectrum from a training set is also tested with and without orthogonal signal correction. We use two data sets, one including five chemical concentrations and the other including ten physical property variables, to compare the performance of partial least squares and modified hybrid least analysis calibration methods. The results show that the hybrid least analysis with a selected training spectrum instead of well-measured pure spectrum still gives good performances, which is a little better than partial least squares.