To obtain the suitable intermediates for stable arylpentazoles, six anilines with multi-electron-donating groups were synthesized. These anilines are reduced from aromatic nitro compounds by using CMC stabilized iron nanoparticles as reductant and [DMFH]H2PO4 as catalyst. This novel method improved the disadvantage of producing wastewater and iron mud and made the reaction more environmental. In addition, these anilines are reduced from azo compounds which was prepared by p-aminobenzene sulfonic acid. Energy barriers for decomposition of the arylpentazoles were also calculated by density functional theory. Based on the energy barriers, we found two main factors affected the stability of arylpentazoles: the number of electron-donating groups and different positions for electron-donating groups on the benzene ring. Results showed that 1) more electron-donating groups usually make the arylpentazoles more stable; 2) both para-substituted and meta-substituted electron-donor groups can obviously increase the stability, especially the effect of previous one is better than the latter one. Due to steric, the stability of all ortho-substituted arylpentazoles decrease.