The electrochemical surface-enhanced Raman spectra (SERS) of 1,4-bis(4-vinylpyridyl)benzene (bvpb) recorded at different electrode potentials with three excitation wavelengths (785, 532 and 473 nm) point out there exists a resonance process involved at more negative voltage with the 785 nm line, giving two strongly enhanced SERS bands at about 1500 and 1150 cm−1. This result agrees with the VIS-NIR transient absorption spectrum characterized by a strong band at 607 nm and a weaker one at 1163 nm, corresponding to the first singlet (S1) and triplet (T1) excited electronic states. The DFT potential energy curve corresponding to the trans–cis (E-Z) isomerization in the S0 state and in the two lowest S1 and T1 excited states, indicates that the S1 state exhibits a significant lower barrier height than S0 state, showing also a S1/S0 conical intersection at a structural conformation in which the vinyl double bond twists by 90°. TD-DFT resonance Raman spectra of the planar and twisted conformation in a simple model of surface complex, Ag20-bvpb, yield that the twisted molecule is able to predict the selected enhancement of the two SERS bands. Therefore, bvpb could act as an electroactive conformational molecular switch under a selected wavelength in nanoelectronic devices.