The present investigation highlights the 2-dimentional design of several interesting super alkali doped borophene derivatives for efficient nonlinear optical (NLO). Borophene (B36) and super alkali units (Li3O) whose combining effects and resulting NLO responses have been evaluated by orienting super-alkali clusters at various sites such as a hub, rim, and bridged around the B36 molecule. The charge analysis is characterized by frontier and natural bond orbital analysis, narrowed HOMO-LUMO band gap, better intramolecular charge transfers. Molecular electrostatic potential surfaces demonstrate enhanced optoelectronic features of these complexes that are viable owing to Li3O adsorption. Singly doped and doubly doped complexes have been considered and their NLO properties have been calculated. Band gap energy reduces about three times when doped with two Li3O. A considerably high figure of merit, first hyperpolarizability (bo) values up to five digits 10611 a. u. for complex A proved that these systems can be utilized as promising candidates in various NLO applications.