Two novel framework compounds, Zn(en)(3)Ag2I4 (1) and Ni(en)(3)Ag2I4 (2), have been synthesized by a self-assembly reaction. Both of them contain an unexpected framework, Ag2I42- with tridymite topolopy, and the discrete M(en)(3)(2+) cations are located in the channels. Their thermal properties and circular dichroism spectra were investigated.