The classical principal component analysis technique is enhanced for reconstruction of reflectance spectra of surface colors from the corresponding tristimulus values under a given set of viewing conditions, i.e., D65 illuminant and 1964 standard observer. In this paper, the number of implemented eigenvectors has been virtually extended from three to six by estimation of another set of tristimulus values under illuminant A and 1964 standard observer. The second set of colorimetric data was predicted by the conventional non-linear regression method and used in the spectral reconstruction to produce a fully determined system in the case of six eigenvectors. The improvement obtained from the proposed modification was examined for the recovery of the reflectance spectra of Munsell color chips as well as ColorChecker DC samples. The performance is evaluated by the mean, maximum and standard deviation of color difference values under other sets of light sources. The values of mean, maximum and standard deviation of root mean square (RMS) errors between the reproduced and the actual spectra were also calculated. Results are compared with those obtained from traditional methods using the principal component analysis (PCA) routine. All metrics show that the suggested method leads to considerable improvements in comparison with the standard PCA approach.