The infrared and Raman spectra of trans-3-phenylacryloyl chloride (TPC) were reported and compared with the theoretical results calculating at B3LYP/6-311++G (d, p) level. Both wavenumbers and intensities obtained from the experimental and theoretical spectra were in good agreement. A complete spectral assignment was made with the aid of potential energy distribution (PED) based on the scaled quantum mechanical (SQM) force field method. This study provided valuable insight for understanding the observed spectral features of TPC. Additionally, the HOMO–LUMO gap, molecular electrostatic potential (MEP) atomic charge distribution, and natural bond orbitals (NBO) were studied theoretically on the same basis set.