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Methodology: The chemical constituents of LCT were identified and quantified using high‐performance liquid chromatography with a diode array detector. A characteristic fingerprint was then established and combined with multivariate statistical analysis of 16 common peaks and eight diterpenoids to identify the quality markers. Introduction: The leaves of Croton tiglium (LCT) have long been used in folk and ethnic medicine in China. Owing to the various regions, the chemical composition and content of LCT may differ, and hence, the quality of medicinal materials may be different. However, quality standards have not yet been established, although some studies have been conducted on their composition. Objectives: To quantitatively compare the chemical constituents of LCT from different areas and establish a quality evaluation of LCT based on quality markers. Results: Eight quality markers selected based on 16 common peaks and three quality markers selected based on eight diterpenoids can distinguish LCT from three regions. The diterpenoids, including 12‐O‐acetylphorbol‐13‐(2‐methylbutyrate) (3), 12‐O‐tiglyl‐4‐deoxy‐4α‐phorbol‐13‐acetate (6), and 12‐O‐(2‐methyl)butyrylphorbol‐13‐tiglate (8), can be used as potential quality markers for the quality evaluation of LCT. Conclusion: Diterpenoids are highly efficient markers for quality evaluation. This study provides robust identification data and lays the foundation for formulating quality standards for LCT. The chemical constituents of the leaves of Croton tiglium (LCT) were identified and quantified using high‐performance liquid chromatography. A characteristic fingerprint was established and combined with multivariate statistical analysis to identify the quality markers. The diterpenoids, including 12‐O‐acetylphorbol‐13‐(2‐methylbutyrate) (3), 12‐O‐tiglyl‐4‐deoxy‐4α‐phorbol‐13‐acetate (6), 12‐O‐(2‐methyl)butyrylphorbol‐13‐tiglate (8), can be used as potential quality markers of LCT. This study provides robust identification data and lays the foundation for formulating quality standards for LCT. [ABSTRACT FROM AUTHOR]