We report a novel type of organic-inorganic hybrid material with rare two-dimensional nonlinear optical (NLO) properties. The density functional theory (DFT) calculations combined with the finite-field (FF) method show that the designed molecules (6,9 organo-derivatives of B10H14) could carry the characteristic NLO properties of both organic and inorganic materials. Interestingly, due to their unique V-shaped structures, they have large off-diagonal first hyperpolarizability tensors or nonlinear anisotropy, which is an advantage in their practical applications over conventional donor-π-acceptor (D-π-A) NLO-phores. The systematic substitutions of terminal donor/acceptor groups as well as the extension of π-conjugation along the V-shape in these derivatives have been evaluated to guide a purpose-oriented synthesis of NLO material. All the systems in the present study have been categorized into Set-I and Set-II with D-π-A-π-D and A-π-D-π-A configurations, respectively. These designed derivatives show large amplitudes of βz values. For example, systems (6,9-[(N[double bond, length as m-dash]C[double bond, length as m-dash]Ph-NO2)2]-B10H12) and (6,9-[((N[double bond, length as m-dash]C[double bond, length as m-dash]Ph)2-NO2)2]-B10H12) have βz amplitudes as large as 34.16 and 276.91 × 10(3) a.u. which are 380 and 3000 times larger than those of a typical NLO molecule of urea, respectively. Remarkably, the substitution of nitrogen atoms with 6,9 hydrogen atoms in decaborane is shown to cause a lone pair back donation to vacant p orbitals of 6,9 boron atoms of the decaborane basket. This p orbital overlapping verticalizes the V-arms of the decaborane derivatives and boosts their nonlinear anisotropies due to their larger off-diagonal tensor components. The nonlinear anisotropy values are significantly larger, ranging from 1 (minimum in system ) to 31.90 (maximum in system ) due to their unique V-shape. Comparison of their efficiencies with standard molecules demonstrates that our designed organic-inorganic hybrid molecules have significant potential as excellent candidates for NLO applications.