Two new 3D hybrid framework iodides, Hmta[(Hmta)Ag4I4] (1; Hmta = hexamethylenetetramine) and [(Hmta)(2)Ag8I6]I-2 (2), have been synthesized under solvothermal conditions. Compound 1 consists of a neutral 3D framework built up from alternation of the tetrahedral Ag4I4 unit and Hmta with dia-b topology. Compound 2 features a 3D cationic framework with flu topology, constructed by cationic [Ag8I6](2+) units linked with Hmta. Tetrahedral Hmta plays crucial structure directing roles in the formation of these 3D frameworks with high symmetry. The temperature-dependent photoluminescent measurement reveals luminescent thermochromism of the compounds, the emission maximum of which shows a gradual blue shift with increasing temperature. The results indicate that 1 is a promising wavelength- and intensity-dependent luminescent thermometer applicable-in two different temperature ranges.