An open-framework indium selenide, [C7H10N][In 9Se14], has been prepared under solvothermal conditions in the presence of 3,5-dimethylpyridine and characterized by single-crystal X-ray diffraction, thermogravimetry, elemental analysis, Fourier tranform IR spectroscopy, and UV-vis diffuse reflectance. The crystal structure of [C 7H10N][In9Se14] contains an unusual building unit, in which corner- and edge-linked InSe45- tetrahedra coexist. The presence of one-dimensional circular channels, of ca. 6 Å diameter, results in approximately 25% of solvent-accessible void space. © 2008 American Chemical Society.