Liquid–air interfaces have extensive implications in different areas of interest because the dynamical processes at the interface can be different from those in bulk. Thus, its characterization, understanding, and control may be pivotal in advancing discoveries. However, characterizing the interface requires special and selective tools to avoid signals from the bulk region. This surface specificity and versatility is achieved by using the second harmonic generation (SHG) responses. This study adopts multiscale simulation methods to evaluate the surface SHG responses of methanol–air interfaces with submonolayer resolution tackled by sequentially using classical molecular dynamics simulations under different temperatures and then employing quantum chemistry methods to compute the molecular first hyperpolarizabilities (β). This approach ensures the configurational diversity required to evaluate the average β values. The main achievements are (i) a quasi-absence of surface sensitivity of the mean polarizability 〈α〉 with values about 2% larger than those obtained in bulk, (ii) conversely, smooth variations on the polarizability anisotropy Δα are observed up to the fourth molecular layer at around 20 Å from the interface, and (iii) narrow interfacial effects on the SHG responses, β(−2ω;ω,ω), which are limited to the first molecular layer (∼3.0 Å) and characterized by a high contrast in the β_ZZZ(−2ω;ω,ω) tensor component between the first and the subsequent layers. Similar trends are obtained at different temperatures or when increasing the number of methanol molecules treated at the quantum chemistry level, indicating the robustness of the approach for describing the dipolar molecular responses of air–liquid interfaces.