N,N′-Propyltriethoxysilane-bis-naphthalenediimide was used to obtain a thermo and photo-active bridged organo polysilsesquioxane gel in DMF. Photophysical and electrochemical measurements revealed a dense diimide π-stacked structure that favors electron-delocalized states and facilitates high yield inherent thermo and photo-generation of radical anions that may be used for photocatalytic purposes, or energy conversion.