The biosynthetic pathway of PP-V, a new monascorubramine homologue, was elucidated by C-13-labeling studies. The [1-C-13] Of acetate was incorporated into 2-, 3a-, 4a-, 6-, 8-, 9-, 11-, 13-, 15-, 17-, and 19-Cs of PP-V, and the [2-C-13], into 3-, 4-, 5-, 8a-, 9a-, 10-, 12-, 14-, 16-, 18-, and 20-Cs. These incorporation patterns coincide with those reported in the biosynthesis of a Monascus azaphilone pigment, monascorubrin.