We have constructed N-piperidinyl-substituted trioxotriangulene (TOT) surface as the catalyst for both the oxygen reduction reaction (ORR) pathways, i.e., 2e− and 4e−. Density functional theory (DFT) is used to study the 2e− and 4e− ORR at two active sites, the O site (oxygen) and N site (nitrogen) in the N-piperidinyl-substituted TOT surface. Reactants and intermediates adsorbate are chemisorbed while the product is physisorbed. The free energy values demonstrate that the O site favors strong catalysis for 2e− and 4e− pathways. In the 4e− reduction pathway, associative mechanism is exothermic and highly feasible. The overpotential values are low at 0.88 V for the O-active site in the associative mechanism in the 4e− pathway. All the results identify the new catalyst, N-pipeTOT surface a potential subject of study for fuel cell applications.