The nonlinear optical response, more specifically the Hyper-Rayleigh Scattering (HRS) response of the Brooker’s merocyanine, has been calculated at the time-dependent density functional theory level and rationalized in terms of the structural changes and polarization effects induced by applied external electric fields. The structural change leads to large changes in the HRS response, while only slight variations were observed due to the polarization effects on the fixed quinoid form. Considering both structural and polarization contributions concurrently, the HRS response is dominated by cooperative behavior of those effects for weak and intermediate electric field strengths. At the same time, the competition between both effects was a crucial factor in the region of strong electric fields. The obtained results can lead to an easier understanding for upcoming studies considering more realistic models of solvents where it is not simple to disentangle these contributions.