Solvent effects on 2-methyl-3-chloromethyl-1,4-naphthoquinone and 2,3-bis(chloromethyl)-1,4-naphthoquinone were investigated using optical absorption and fluorescence emission techniques and the orientation of 2-methyl-3-chloromethyl-1,4-naphthoquinone on a silver surface was studied by surfaceenhanced Raman scattering (SERS). The observed spectral shift and the bandwidth of the optical absorption spectrum reveal the changes in dipole moment and the solvent reorganization energy in the excited state. The observed fluorescence quantum yield influences the weak intermolecular hydrogen bond and the dipole-dipole interaction in the excited state. Fluorescence polarization measurements provide the faster rotational relaxation of 2-methyl-3-chloromethyl-1,4-naphthoquinone and 2,3-bis(chloromethyl)-1,4-naphthoquinone in the excited state. SERS studies suggest that the orientation of 2-methyl-3-chloromethyl-1,4-naphthoquinone on a silver surface is stand-on.