In this paper the application of destruction neutron activation analysis technique to soil samples of complex matrix is described. The chemical group separation based on a combination of distillation and anion-exchange was used. Five-fractions of As-Se, Hg-Sb, Cr-La-Sc, Co-Fe and Zn-Cd-Mo were measured by both the Ge(Li) detector connected to the computer and the NaI(Tl) well-type detector. The combined use of the two systems gives full scope to the high resolution of the Ge(Li) detector in the analysis of samples of complex matrix and the highest sensitivity and the high efficiency of NaI(Tl) detector in the analysis of trace elements at very low concentration. The results of 12 trace elements of the soil samples from Beijing and Nanjing determined with the method mentioned above were obtained.