Cementitious materials containing admixtures such as industrial waste or by-products is highly expected for environment and sustainable development. These materials have problems with slow hydration, and the use of a hydration accelerator is an effective solution. Therefore, in this study, authors focused on synthesized C-S-H among hydration accelerators, detailed characterization was carried out on the synthesized C-S-H with different Ca/Si ratio(C/S), and the effect of this C-S-H on the initial hydration reaction of alite was investigated. As a result, it was elucidated that seeding greatly influences the precipitation of C-S-H rather than the dissolution of alite. Moreover, it was confirmed that addition of synthesized C-S-H with low C/S promotes initial C-S-H precipitation, while hydration rate and amount of C-S-H precipitation at the late hydration stage and MCL of generated C-S-H don't depend on C/S of synthesized C-S-H. According to these results, addition of synthesized C-S-H with low C/S to cementitious materials may be solve the problem of initial strength of cementitious materials using admixtures such as industrial waste or by-products.