Because of similarity explosive component elements and exist same molecular bound, choosing a suitable separation methods have been complicated. LIBS and Raman spectroscopy methods are useful in this field. Raman signal is weak for small amount and LIBS required to statistical method for identification these materials. In this research, correlation coefficient values obtain from intensity of two methods was calculated for RDX, TNT, HMX and PETN. Suitable method for detection of pair of them have been proposed.