Eight major pigments have been isolated from commercial Monascus pigments. The structural data on the pigments were obtained using NMR, MS, and semisyntheses. The pigments were characterized as alanine or aspartate derivatives of the orange pigments of Monascus, monascorubrin (1) and rubropunctatin (2), which have an azaphilone structure. The semisyntheses revealed that the amino acid units of the isolated compounds were the D-forms as well as the L-forms.