The synthesis of isotope labeled cyclotetramethylenetetramine (HMX) and its precursor，and the application of isotope tracing technique in the synthesis of HMX by acetic anhydride method and non-acetic anhydride method were summarized. The application of isotope tracing technology in the biodegradation process of energetic contaminants were also introduced. The study shows that HMX prepared from the acetic anhydride method tends to restructuring mechanism; HMX prepared from the TAT and DADN method is more inclined to the step-by-step degradation mechanism. HMX-¹⁴C can be used for the quantitative and qualitative analysis of biological degradation products accurately.