In case of glass ceramics and powder preparation from the metalakoxide solutions, metalakoxide solutions with a various species of alkoxy groups have unique characteristics. Therefore, in this study, the mixing ability of homogeneous sol, gel morphology and physical properties of gels were investigated by the changes in terms of the different four alkoxy groups, CH3-, C2H5-, i-C3H7-n-C4H9-, along with the catalyst for the purpose of the observation about the homogenous transition range from sol to gel. As a result, when the fixed condition was mol ratio of H2O/Si(OR)4=2.0 and variables were batch composition and addition amount of catalyst, the characteristics of Tetra-normal-Butoxysilane and Tetra-iso-propoxysilane systems had very narrow sol-gel conversion region than Tetramethoxysilane and Tetraethoxysilane system. And silicon-alkoxide, systems having narrow sol-gel conversion region were enlarged by addition of catalyst. In viewpoint of the weight loss of gel produced by hydrolysis of silicon alkoxide systems with different four alkoxy groups, the amounts of weight loss of gel containing large molecular alkoxy groups were much more than those of small molecular alkoxy group.