The favorable excited-state dynamics, nonlinear optics, and extraordinary phototheranostic capabilities of conjugated metallaaromatics are attractive topics of research. A promising and multifunctional photosensitizer, double-phenanthroline-carbolong DPC, was investigated comparatively. It featured strong two-photon absorption (2PA) properties within the near-infrared (NIR) range and a maximum 2PA cross section ~7417 GM at 770 nm in MeOH. Time-dependent density functional theory and ultrafast excited-state dynamics illustrated that fast charge transfer coupled with intersystem crossing to the stable triplet state outcompeted the radiative decays. The “three-in-one” phototherapeutic effect owned the NIR-wavelength 2PA excitation, photodynamic therapy, and photothermal therapy in DPC were illustrated subsequently. The significant contribution from the intrinsic intramolecular charge communication along the DPC skeleton provided the possibility for moderate photothermal conversion (η=36.8%) and photodynamic synergistic therapy (ΦΔ=8.4%). Interestingly, the singlet oxygen generation from DPC was also endowed when irradiated at two-photon exciting wavelengths. In vitro experiments demonstrated the synergistic phototoxicity of DPC in 4T1 cancer cells. Present work offers insights into the extraordinary carbolong metallaaromatics and highlights their potential applications in the fields of nonlinear optics and multifunctional phototheranostics.