Electrochemically grown cadmium sulfide (CdS) nanorod arrays were studied with Raman spectroscopy. The resonant Raman spectroscopy unravels the enhanced electron-phonon interaction up to the fifth-order multiphonon process in the vertically aligned CdS nanorods after annealing. Resonant Raman scattering at room temperature reveals a surface phonon mode at 253 cm−1 in the annealed nanorod. This unprecedented observation is accounted for by the lateral confinement in the nanorod whose average aspect ratio is approximately 5. An intersubband transition near 3000 cm−1 is also observed. These results point to important optoelectronic applications of this material.