In the present research, Raman spectra of 31 fatty alcohols were calculated by B3LYP/6-31G (d) and verified by taking methanol for example. The study results indicate that B3LYP/6-31G (d) is an effective approach for the fatty alcohols Raman spectra calculated. The vibrational assignment and Raman spectra features of 6 unbranched alcohols were discussed and the vibrating peaks derived from stretching vibration by C—O were chosen as the research target selection, and the multiple principal component regression models were established and validated with the parameters including polarizability, thermodynamic and energy parameters of the above unbranched alcohols. There exists significant correlation between the vibrating peaks derived from stretching vibration by C—O of fatty alcohols and the parameters (sig.=0.015). This study will benefit the Raman spectra research of homologs.