Four endogenous products of oxidative bilirubin degradation were isolated and fully characterized. The constitutional isomers belong to the propentdyopents (PDPs). Their structures and further oxidative transformations to biologically active bilirubin oxidation end products (Z-BOXes) are reported. Using liquid chromatography-mass spectrometry protocols, PDPs were detected in human bile and gallstones. Given the recent interest in BOXes as effectors in cerebral vasospasms and liver dysfunction, co-occurring PDPs represent an additional potentially active compound class to be considered.