A series of alkylammonium tris(oxalato)silicate compounds [R(4)N](2)[Si(C2O4)(3)], where R(4)N(+) = (CH3N+ (1), (CH3)(3)(C6H5N+ (2), (CH3CH2N+ (3), (CH3CH2CH2N+ (4), (CH3(CH2)(3)N+ (5), and (CH3(CH2)(5)N+ (6), were prepared as precursors to microporous materials. Compounds 1 and 2 were structurally characterized by X-ray crystallography. [(CH3)(4)N](2)[Si(C2O4)(3)] and [(CH3)(3)(C6H5)N](2)[Si(C2O4)3] crystallize in the monoclinic P2(1)/c and P2(1)/n space groups respectively with a = 17.631(2) Angstrom, b = 10.1984(9) Angstrom, c = 12.095(1) Angstrom, beta = 108.810- (8)degrees, and Z = 4 for 1 while a = 8.855(2) Angstrom, b = 18.050(2) Angstrom, c = 17.102(2) Angstrom, beta = 95.24(1)degrees, and Z = 4 for 2. The oxalate (ox) ligands are arranged in an octahedral fashion around the silicon. Thermal decomposition of the oxalate complexes 1-6 results in amorphous silica. Single point determination of the surface area indicates a greater surface area is obtained as the size of the alkylammonium ions increases.