We present a computational model for electrochemical surface-enhanced Raman scattering (EC-SERS). The surface excess of charge induced by the electrode potential (Vel) was introduced by applying an external electric field to a set of clusters [Agn]q with (n, q) of (19, ±1) or (20, 0) on which a molecule adsorbs. Using DFT/TD-DFT calculations, these metal-molecule complexes were classified by the adsorbate partial charge, and the main Vel-dependent properties were simultaneously studied with the aid of vibronic resonance Raman computations, namely, changes on the vibrational wavenumbers, relative intensities, and enhancement factors (EFs) for all SERS mechanisms: chemical or nonresonant, and resonance Raman with bright states of the adsorbate, charge-transfer (CT) states, and plasmon-like excitations on the metal cluster. We selected two molecules to test our model, pyridine, for which Vel has a remarkable effect, and 9,10-bis((E)-2-(pyridin-4-yl)vinyl)anthracene, which is almost insensitive to the applied bias. The results nicely reproduced most of the experimental observations, while the limitations of our approach were critically evaluated. We detected that accounting explicitly for the surface charges is key for EC-SERS models and that the highest calculated EFs, up to 107 to 108, are obtained by interstate coupling of bright local excitations of the metal cluster and CT states. These results highlight the importance of nonadiabatic effects in SERS and the capabilities of EC-SERS as a technique with potential to study excited-state coupling by tuning the CT and plasmon-like states by manipulating Vel.