The present investigation highlights the 2-dimentional design of several interesting super alkali doped borophene derivatives for efficient nonlinear optical (NLO). Borophene (B 36 ) and super alkali units (Li 3 O) 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 B 36 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 Li 3 O 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 Li 3 O. A considerably high figure of merit, first hyperpolarizability ( o ) 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.