Xanthobilirubic acid, 5‐[1,5‐didehydro‐3‐ethyl‐4‐methyl‐5‐oxo‐2H‐pyrrol‐2‐ylidene)methyl]‐2,4‐dimethyl‐1H‐pyrrol‐3‐propanoic acid, its methyl ester, amide, N‐methylamide and dimethylamide, and kryptopyrromethenone have been synthesized and characterized spectroscopically. In d6‐DMSO solution all pyrromethenones were monomeric, with lactam and pyrrole N‐Hs H‐bonded to solvent. In deuteriochloroform, the pyrromethenones preferred a dimeric form, with intramolecular H‐bonding between the lactam C = 0 of one unit and the lactam and pyrrole N‐Hs of the second.