The biosynthetic pathway of sterigmatocystine, a metabolite of Aspergillus versicolor, was studied by labeling the metabolite with ^<13>CH_3^<13>CO_2Na. The ^<13>C-nmr spectrum revealed that sterigmatocystine is formed from tetraketide through pathway (b) as shown in Fig. 1. The same technique was also applied to investigate the biosynthesis of penicillic acid. The result shown in Fig.3, pathway (a), was completely in agreement with the conclusion obtained by Mosbach.