Lucigenin (N,N′‐dimethyl‐9,9′‐biacridinium nitrate) 1 on heating under reflux in protic solvents in the presence of amines gives rise to the N,N′‐dimethyl‐9,9′‐biacridylidene 2 (DBA) or protected hemiaminal N‐methoxymethyl‐9,9′‐bi‐acridylidene 3. On the other hand acid hydrolysis and synchronous oxidation of hemiaminal 3 followed by reaction of monomethyl‐biacridinium nitrate 4 with sodium hydroxide in methanol or water leads to biacridine 5 (overall yield ca. 33%).