The direct fusion of a diphenylmethane segment to a Ni^II 5,10,15‐triarylporphyrin with three linkages furnished an air‐ and moisture‐stable neutral radical through unexpected and spontaneous oxidation. This radical was demetalated by treatment with H₂SO₄ and CF₃CO₂H to provide the corresponding free‐base radical. These porphyrin radicals are very stable owing to spin delocalization and have been fully characterized through UV/Vis/NIR absorption spectroscopy, X‐ray crystallographic analysis, magnetic susceptibility measurements, electrochemical studies, laser‐based ultrafast spectroscopic studies, and theoretical calculations. They were chemically oxidized and reduced to the corresponding cation and anion but did not react with hydrogen‐atom donors.