The second-order nonlinear optical (NLO) responses of a donor-acceptor stenhouse adduct (DASA) are investigated by using a computational approach combining molecular dynamics simulations and density functional theory (DFT) calculations. Specific force fields for the open and closed photoswitching forms are first parameterized and validated according to the Joyce protocol, in order to finely reproduce the geometrical features and potential energy surfaces of both isomers in chloroform solution. Then, DFT calculations are performed on structural snapshots extracted at regular time steps of the MD trajectories to address the influence of the thermalized conformational dynamics on the NLO responses related to hyper-Rayleigh scattering (HRS) experiments. We show that accounting for the structural dynamics largely enhances the HRS hyperpolarizability (βHRS) compared to DFT calculations considering solely equilibrium geometries, and greatly improves the agreement with experimental measurements. Furthermore, we show that the NLO responses of the NLO-active open form are correlated with the bond order alternation along the triene bridge connecting the donor and acceptor moieties, which is rationalized using simple essential state models.