The geometrical structures of several Raman probe molecules were optimized using density functional theory (DFT) of the hybrid density functional B3LYP method and 6-311++G** basis set. Their energy gap, nucleus independent chemical shift(NICS), polarizability and vibration spectrum were studied. The theoretical results showed that: 4-MPY, MBA and PATP had planar structures, the angle of BDT between S-H and benzene ring plane was 20.2°, and the 4-MBT was 39.6° ; they all have a strong aroma and a large value of polarization. The order of the average of molecular hyperpolarizability tensor was BDT>4-MBT>4-MBA>4-MPY>PATP, and the trends of polarizability anisotropy invariant were 4-MBA>4-MBT>BDT>PATP>4-MPY.