A rhodium(III)-porphyrin zirconium metal-organic framework (Rh-PMOF-1(Zr)) has been prepared from the self-assembly of a Rh-based metalloporphyrin tetracarboxylic ligand Rh(TCPP)CI (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with ZrCl4. The framework of Rh-PMOF-1 is stable up to 270 degrees C as disclosed by the variable-temperature powder X-ray diffraction (VT-PXRD) measurements, and possesses good chemical stability over a wide range of solvents including water. The single-crystal structural analysis reveals that Rh-PMOF-1 contains 3D channels (1.9 x 1.9 nm(2)), and the Rh-porphyrin units are exposed to the cavities. The calculation based on the N-2 adsorption at 77 K shows Rh-PMOF-1(Zr) has a high BET surface area (3015 m(2)g(-1)). The luminescence decay of Rh-PMOF-1 is well fitted to a tri-exponential curve featuring a long average lifetime of 207 mu s at 298 K under vacuum, which represents a rare example of room-temperature phosphorescence of Rh-porphyrin complexes. Under 1 atm, it displays CO2 uptake up to 42, 53 and 98 cm(3)g(-1) at 308, 298 and 273 K, respectively. Catalytic results show that, under the visible light (>= 400 nm) irradiation without any additional photosensitizer, Rh-PMOF-1 is powerful to catalyze CO2 reduction to the formate ion with up to 99% selectivity, and can be recycled and reused for 3 runs. Theoretical study was further carried out to reveal the energy levels of the frontier orbitals of Rh-PMOF-1 and the preferred binding sites of CO2 in the framework.