5,6‐Dimethylbenz[a]phenazine (4), an aza analogue of the carcinogenic 5,6‐dimethylbenz‐[c]acridine has been obtained by a 1,1‐dehydration‐rearrangement (Wagner‐Meerwin type) from 5,5‐dimethyl‐6‐hydroxy‐5,6‐dihydrobenz[a]phenazine (3). The alcohol 3 was obtained from the hydrogenation of the corresponding ketone 2 which was prepared in two ways: Method A, the oxidation of 5,5‐dimethyl‐5,6‐dihydrobenz[a]phenazine (1); Method B, the hydrolysis of the 6,6‐dibromo derivative 5 of 1.