We apply a multivariate statistical method to the Phoebe spectra collected by the VIMS experiment onboard the Cassini spacecraft during the flyby of June 2004. The G-mode clustering method, which permits identification of the most important features in a spectrum, is used on a small subset of data, characterized by medium and high spatial resolution, to perform a raw spectral classification of the surface of Phoebe. The combination of statistics and comparative analysis of the different areas using both the VIMS and ISS data is explored in order to highlight possible correlations with the surface geology. In general, the results by Clark et al. [Clark, R.N., Brown, R.H., Jaumann, R., Cruikshank, D.P., Nelson, R.M., Buratti, B.J., McCord, T.B., Lunine, J., Hoefen, T., Curchin, J.M., Hansen, G., Hibbitts, K., Matz, K.-D., Baines, K.H., Bellucci, G., Bibring, J.-P., Capaccioni, F., Cerroni, P., Coradini, A., Formisano, V., Langevin, Y., Matson, D.L., Mennella, V., Nicholson, P.D., Sicardy, B., Sotin, C., 2005. Nature 435, 66-69] are confirmed; but we also identify new signatures not reported before, such as the aliphatic CH stretch at 3.53 ??m and the ???4.4 ??m feature possibly related to cyanide compounds. On the basis of the band strengths computed for several absorption features and for the homogeneous spectral types isolated by the G-mode, a strong correlation of CO2 and aromatic hydrocarbons with exposed water ice, where the uniform layer covering Phoebe has been removed, is established. On the other hand, an anti-correlation of cyanide compounds with CO2 is suggested at a medium resolution scale. ?? 2007 Elsevier Inc. All rights reserved.