To further understand the metabolic transition between primary and secondary metabolism in the process of streptolydigin biosynthesis by Streptomyces lydicus AS 4.2501,the metabolomic analysis of metabolites of various cultural phases was performed by ESI-MS and principal components analysis(PCA).The results showed that metabolomics could be used to discriminate various types of metabolites.Especially,major separation between primary and secondary metabolism was achieved in third principal component(PC3).Combining tandem mass spectrometry(MS/MS) and the reports of references for characterizing biomarkers,phospholipids and proteins were found to contribute most to the spectral information.