The widespread use of nonlinear optical (NLO) materials for contemporary technologies has sparked intense interest in their production with the creation of materials with a continuous endeavor. In this theoretical study, we investigate the NLO responses of doped superalkali (SA) metal salts with planar boron sheets (PBSs). We consider four different substrates (B[Formula: see text], B[Formula: see text]F3, B[Formula: see text], and B[Formula: see text]F3) to create 12 new surfaces (1-12) by doping SAs (Li2F, Li2OF, Li2O2) with them. We optimize the geometries of these surfaces and analyze their frontier molecular orbitals (FMOs) and natural bond orbitals (NBO) to obtain insights into their global chemical reactivity. We also examined their NLO responses ranging as 1.22–[Formula: see text], 3.39–[Formula: see text], and [Formula: see text][Formula: see text]e.s.u. Our results reveal that the doped surfaces exhibit stronger NLO responses compared to the undoped surfaces, and that the strongest NLO response is found in the B[Formula: see text]F3-doped surface. The role of various segments in FMOs is investigated using the TDOS and PDOS spectral analyses. To comprehend the relationship between the SA and the B[Formula: see text]F3 substrates molecule more effectively, non-covalent interaction (NCI) investigation is carried out. Additionally, Time-dependent DFT (TD-DFT) simulations are done for UV–Vis analysis to observe significant redshifts up to 1050[Formula: see text]nm. All the SA-doped surfaces are thermodynamically stable NLO materials with improved NLO responses, so these materials are proposed to be used during the construction of advanced NLO responses.