Metamerism is one of the major fundamental phenomena of the visual system and important Subject in color Matching. Because metamer samples are basic to most colorimetric issues, both in theory as well as in practice,they have been considerably analysed. There has been a large amount of literature discussing about the Reflectance properties sets.the results explained in these literatures are difference due to various method of metamer samples generation in the recent researches metamers are generated using new methods based on statistical information of the measured set. In the present research, principal component analysis(PCA) is used to spectral analysis of metamers.As obtained results indicate, there are significant differences between principal components of metamer and matched samples. Also, paramer samples were analysis by this technique and results of the principal components showed a large differences between these pairs and matched pairs.