The effect of C12A7 and OH group on the synthesis of C3A by the sol-gel process using aluminum-sec-butoxide and calcium nitrate was studied. C3A by sol-gel method was compared with C3A obtained by the conventional method with respect to their reactivity of formation and crystal size. The sol-gel process for initial formation of C12A7 and C3A at lower temperature (1100, 1200$^{circ}C$) was superior, but that for complete crystallization of C3A at higher temperature (1300, 1400$^{circ}C$) was inferior to oxide mixture process. When heat treated under the atmosphere oxygen-free dried nitrogen eliminate the influence of OH group in C12A7, the reactivity of C3A from sol-gel sample incorporated OH group were poor, whereas that from oxide mixture sample showed remarkable effect. The poor crystallization of C3A at higher temperature is presumed to be due to the fact that incorporated OH group in C12A7 formed at lowr temperature might interrupt the diffusion of CaO to C12A7 to from C3A. The crystal size and the hydration characteristics of both C3A obtained by different processes exhibited almost the same results.