Materials　capable　of　efficiently　converting　near-infrared　(NIR)　light　into　heat　are　highly　sought　after　in　biotechnology.　In　this　study,　two　new　three-dimensional　(3D)　porphyrin-based　metal-organic　frameworks　(MOFs)　with　a　sra-net,　viz.　CoTCPP-Bi/NiTCPP-Bi,　were　successfully　synthesized.　These　MOFs　feature　bismuth　carboxylate　nodes　interconnected　by　metalloporphyrinic　spacers,　forming　one-dimensional　(1D)　arrays　of　closely　spaced　metalloporphyrins.　Notably,　the　CoTCPP-Bi　exhibits　an　approximate　Co⋯C　distance　of　3　Å,　leading　to　enhanced　absorption　of　NIR　light　up　to　1400　nm　due　to　the　presence　of　strong　interlayer　van　der　Waals　forces.　Furthermore,　the　spatial　arrangement　of　the　metalloporphyrins　prevents　axial　coordination　at　the　centers　of　porphyrin　rings　and　stabilizes　a　CoII-based　metalloradical.　These　characteristics　promote　NIR　light　absorption　and　non-radiative　decay,　thereby　improving　photothermal　conversion　efficiency.　Consequently,　CoTCPP-Bi　can　rapidly　elevate　the　temperature　from　room　temperature　to　190　°C　within　30　seconds　under　0.7　W　cm−2　energy　power　from　808　nm　laser　irradiation.　Moreover,　it　enables　solar-driven　water　evaporation　with　an　efficiency　of　98.5%　and　a　rate　of　1.43　kg　m−2　h−1　under　1　sun　irradiation.　This　research　provides　valuable　insights　into　the　strategic　design　of　efficient　photothermal　materials　for　effective　NIR　light　absorption,　leveraging　the　principles　of　aggregation　effect　and　metalloradical　chemistry.　©　2024　The　Royal　Society　of　Chemistry.