Based on the combination of novel carbon material graphynes (GYs) and superalkalis (OM₃), a class of graphyne superalkali complexes, OM₃⁺@(GY/GDY/GTY)^– (M = Li, Na, and K), have been designed and investigated by density functional theory method. Computational results reveal that these complexes with high stability can be regarded as novel superalkali salts of graphynes due to electron transfer from OM₃ to GYs. For second order nonlinear optical response, these superalkali salts exhibit large first hyperpolarizabilities (β₀). Two important effects on β₀ values are found, namely the atomic number of alkali atom in superalkali and the pore size of graphyne. Integrating the two effects, the selected combination of OLi3 with large pore size GTY can bring the considerable β₀ value (6.5×10⁵ au), which is a new record for superatom-doped graphynes. In the resulting complex, the OLi₃ molecule is located at the center of the pore of GTY, forming a planar structure with the highest stability among these salts. Besides large β₀ values, these superalkali salts of graphynes have deep-ultraviolet working region, hence can be considered as a new kind of high-performance deep-ultraviolet NLO molecules.