<p>The performance of 12 X₁₆Y₁₆ nanoclusters (X/Y = Al/N, Al/P, B/N, B/P, Be/O, C/Ge, C/Si, C/C, Ga/P, C/N, Ga/N, N/P) as anode materials for Li/Na-ion batteries was investigated by density functional theory. Firstly, the structures of 12 nanoclusters with <i>T</i>_d symmetry were optimized using the B3LYP method with a 6-311G (<i>d</i>, <i>p</i>) basis set. The symmetry of Al₁₆P₁₆ and C₁₆N₁₆ was changed to <i>D</i>_2d and S₄, while the others remained unchanged after optimization. The cohesive energies were calculated, which were used as a stability indicator for the 12 X₁₆Y₁₆ structures. Secondly, the possible adsorption sites of Li/Li⁺ and Na/Na⁺ adsorbed at 12 nanoclusters were predicted through molecular electrostatic potential analysis, and the adsorption energies and <i>V</i>_cell values were calculated. The stability ranking of the adsorbed complexes could be predicted by formation energy. It was found that Be₁₆O₁₆ exhibited preferential adsorption for Li⁺ with Δ<i>E</i>_g of −24.8%, yielding the highest voltage of 1.03 V, while B₁₆N₁₆ demonstrated optimal adsorption energy toward Na⁺ with Δ<i>E</i>_g of −28.6%, accompanied by the voltage of 0.82 V. The partial density of states (PDOS) for Li⁺/Be₁₆O₁₆ and Na⁺/B₁₆N₁₆ revealed that Li⁺(s) and Na⁺(s) states stabilized the lowest unoccupied molecular orbital (LUMO) energy levels, while O(<i>p</i>) and N(<i>p</i>) states lowered the highest occupied molecular orbital (HOMO) energy levels of Be₁₆O₁₆ and B₁₆N₁₆, respectively. Finally, the influence of solvation effects on battery performance was considered. It was found that the battery voltages were increased when the specify solvent was used, with the voltage of Li/Be₁₆O₁₆ rising from 1.03&#xa0;V to 2.93 V, and that of Na/B₁₆N₁₆ increasing from 0.82&#xa0;V to 0.89 V.</p> Graphical Abstract <p>DFT screening of 12 X₁₆Y₁₆ nanoclusters identifies Be₁₆O₁₆ and B₁₆N₁₆ as superior anode materials for Li/Na-ion batteries, respectively. They exhibit high Li⁺/Na⁺ adsorption energies and significant voltage enhancement under solvation. The battery could be regarded as an appliance, with electrons transferring from the cathode to the anode during charging. This led to an increase in electron density at the X₁₆Y₁₆, thereby promoting more Li⁺/Na⁺ suitable adsorption at the anode. During discharging, electrons moved from the anode to the cathode, where the electrons were lost from Li/Na owing to the oxidation reaction at the anode, and the released Li⁺/Na⁺ migrated toward the cathode.</p>