Wet denitrification is a promising approach to control nitrogen oxides (NOx) produced in fossil fuel combustion. Yet, the highly concentrated nitrite (NO2-) wastewater generated poses a major threat to the aqueous environment. Here, iridium nanoclusters (d = 1.63 nm) deposited on TiO2 were applied for NO2- reduction to ammonia (NRA), showing an exceptional NH4+ selectivity of 95% and a production rate of 20.51 mgN·L-1·h-1, which held significant potential for NO2- wastewater purification and ammonia resource recovery. Notably, an interesting non-first-order NO2- hydrogenation kinetics was observed, which was further confirmed to result from the competitive adsorption mechanism between H2 and NO2- over iridium. The NRA pathways on the Ir(111) surface were explored via density functional theory calculations with the NO2-* → NO* → HNO* → HNOH* → H2NOH* → NH2* → NH3* identified as the most energetically favorable pathway and the NO* → HNO* confirmed as the rate-determining step. In situ DRIFTS further experimentally verified the generation of HNO* intermediate during NO* hydrogenation on Ir(111). To verify NRA kinetics at varied NO2- concentrations or H2 pressures, a kinetic model was derived based on the Langmuir-Hinshelwood competitive adsorption mechanism. These findings provide mechanistic insights into the NRA pathways on Ir nanocatalysts, which will be beneficial for wet denitrification waste stream decontamination and valorization.