Hexahydropyrrolo[3,4-b]-7-azaindole derivatives were synthesized from 3-nitroazaindoles and 1,3-dipole which was generated in situ through [3+2] dipolar cycloaddition. The synthetic conditions of hexahydropyrrolo[3,4-b]-7-azaindole derivatives were optimized, using methylene chloride as solvent, and with the reaction taking place at room temperature for 1 h. The yield under such conditions was 85%～95% and the diastereoselectivity was over 99:1. The structures of these compounds were characterized by 1H-NMR, 13C-NMR and high resolution mass spectrometry analysis. The results showed that target structures products were obtained. Furthermore, X-ray diffraction was used to analysis the structures of compound (S,S)-6-benzyl-4b-nitro-8-tosyl-4b,5,6,7,7a,8-hexahydropyrrolo[3',4':4,5]pyrrolo[2,3-b]pyridine (Ⅲa). The result showed that the relative configuration of chiral center was (S,S) or (R,R).