Microcosm studies were conducted to demonstrate the effectiveness of tetrabutoxysilane (TBOS) as a slow-release anaerobic substrate to promote reductive dehalogenation of trichloroethylene (TCE). The abiotic hydrolysis of TBOS and tetrakis(2-ethylbutoxy)silane (TKEBS), and the biotic transformations of the hydrolysis products from both were also investigated. Comparison of TCE reductive dehalogenation was performed with microbial communities stimulated from three different sites: Site 300 Lawrence Livermore National Laboratory (LLNL), CA, Point Mugu Naval Weapons Facility, CA, and the Evanite site in Corvallis, OR. Poisoned microcosms showed that 1 mol of TBOS slowly and abiotically hydrolyzes to 4 mol of 1-butanol, while the live microcosms showed the 1-butanol ferments to butyrate and/or acetate, producing H2. The hydrolysis of TBOS and TKEBS was abiotic and not enhanced by biotic processes under the anaerobic conditions of these tests. Hydrogen consumption was correlated with reductive dehalogenation, indicating it served as an electron donor for reductive dehalogenation. TBOS was found to be a slow-release anaerobic substrate to support long-term dechlorination of TCE to ethylene in Point Mugu microcosms, and in the LLNL microcosm bioaugmented with the Evanite culture. Electron mass balances showed most of the electron flow went into the creation of organic acids, especially acetate, and the production of methane. Electron efficiencies for reductive dechlorination were as high as 14% based on the electrons used for dechlorination to the total electrons associated with the mass of TBOS and TKEBS hydrolyzed. Rates of TBOS hydrolysis increased with greater TBOS concentrations as a light nonaqueous-phase liquids (LNAPL). These results indicate that TBOS has promise as an effective anaerobic substrate for remediating a wide range of CAH concentrations at different CAH contaminated sites.