Porphyrin derivatives and their analogs show great potential as near-infrared (NIR) chromophores, paving the way for innovative optical materials across various fields, including light-harvesting, sensing, and therapeutic applications. Structural modifications, such as core expansion, peripheral fusion, and chromophore array, have shifted the light-responsive wavelength into the NIR window while maintaining high photo- and chemical stability. Since the discovery of the porphyrin isomer known as N-confused porphyrin, our research group has focused on developing a series of π-conjugated porphyrin analogs incorporating “N-confused” pyrrole rings. These unique structures enhance metal coordination ability, which is crucial for triggering molecular orbital mixing and tuning in N-confused porphyrinoids. This leads to remarkable NIR optical properties and controlled excited-state dynamics. This presentation will highlight the recent advancements in bis-metal complexes of N-confused porphyrinoids that exhibit NIR functionality, following a brief overview of the chemistry of N-confused porphyrin and its contracted or expanded analogs.[1, 2] Unique properties—including distinct emission and photoacoustic signals in the second and third NIR regions, stable π radicals, an exceptionally high twophoton absorption cross-section upon second NIR pulse irradiation, and numerous metal-ligand chargetransfer transitions via d-π orbital interactions—are all attributed to the molecular orbital features.