The crystal structure of bromo(tetraphenylporphyrin)iron(III), BrFe{C20N4H8(C6H5)4}, has been determined at 295 K by X-ray diffraction and refined by least squares to a residual of 0.052 (2689 ?observed? reflections). Crystals are monoclinic, P21/c, a 10.191(2), b 16.121(5), c 23.223(4) Ǻ, β 115.34(1)�, Z 4. The iron atom lies out of the N4 plane of the porphyrin ligand by 0.49 Ǻ, being 2.069 Ǻ; the apex of the five-coordinate square-pyramidal coordination sphere about the iron is occupied by the bromine [Fe-Br 2.348(2) Ǻ].