Bimetallic glycolato silicates of the form M2 Si2(OCH2CH2O)5 where M is an alkali metal, can be synthesized directly from SiO2, ethylene glycol and MOH. Further reaction with HO(CH2CH2O)4H, PEG4, transforms these compounds into rheologically useful polymers. These polymers offer considerable potential for processing novel silicate glass shapes, e.g. thin films, fibers and membranes, from relatively inexpensive precursors materials. In this paper, we describe pyrolysis studies on the model compound Li2 Si2(OCH2CH2O)5 as a prelude to determing the utility of the polymeric precursors. These studies delineate the effects of temperature on the decomposition processes whereby the glycolato silicate transforms into almost phase pure, crystalline Li2O-2SiO2. This work is contrasted with previous pyrolysis studies on K2 Si2(OCH2CH2O)5.