The Hugoniot data of naphthalene under shock compression were measured by using a two-stage gas gun, and the D-u line was obtained at an impact pressure of 13.7 GPa: D = 2.102 (±0.09) + 1.865 (±0.066) up. Furthermore, the Raman spectra of naphthalene were acquired under impact pressures of 2.33 GPa and 3.55 GPa by utilizing a transient Raman spectroscopy system. Seven intramolecular vibration modes were observed, and the corresponding Raman peaks shifted blue with the increase of impact pressure. However, no anomalous phenomena such as peak splitting or disappearance were detected, indicating that the stability of naphthalene within the applied pressure range and the frequency shift of shock-compressed naphthalene obviously depend on the density rather than the pressure.