A novel family of IrIII complexes bearing a pyridoannelated N‐heterocyclic carbene is herein described. The target compounds 1–5 are straightforwardly prepared and fully characterized. Comprehensive investigation of their optical properties reveals a rare case of dual emission ascribed to two excited states localized onto different portions of the molecule, as confirmed by both optical spectroscopy and time‐dependent density functional calculations including spin‐orbit coupling. The cytotoxicity against cancer cell lines is investigated as well. Remarkably, 2–5 show up to 50‐fold higher anticancer activity in vitro compared to oxaliplatin market drug with concentration values required to reduce by 50 % the cell viability (IC50) in the low μM range. Finally, in‐depth biological investigation on the most cytotoxic compound 4 reveals its powerful mitochondrial dysfunctioning activity and efficient reactive oxygen species production, associated with apoptosis as the mechanism of cell death.