Enhanced reactivity of the methyl group of 2‐t‐butyl‐5‐methyl‐1,3,4,6,9b‐pentaazaphenalene allowed acetic anhydride‐catalyzed condensation reactions with several aromatic aldehydes, and base‐catalyzed alkylation reactions with several alkyl halides to take place, albeit in low yields. Of the many nucleophiles tried, only salts of carboxylic acids, in the presence of 18‐crown‐6, were able to displace bromine from 2‐(bromomethyl)‐5‐methyl‐1,3,4,6,9b‐pentaazaphenalene.