This paper presents a study on the carbonation behaviors of hydraulic and non-hydraulic calcium silicate phases, including tricalcium silicate (3CaO center dot SiO2 or C3S), gamma-dicalcium silicate (gamma-2CaO center dot SiO2 or gamma-C2S), beta-dicalcium silicate (beta-2CaO center dot SiO2 or beta-C2S), rankinite (3CaO center dot 2SiO(2) or C3S2), and wollastonite (CaO center dot SiO2 or CS). These calcium silicate phases were subjected to carbonation reaction at different CO2 concentration and temperatures. Thermogravimetric analysis (TGA) tests were performed to quantify the amounts of carbonates formed during the carbonation reactions, which were eventually used to monitor the degree of reactions of the calcium silicate phases. Both hydraulic and non-hydraulic calcium silicates demonstrated higher reaction rate in case of carbonation reaction than that of the hydration reaction. Under specific carbonation scenario, non-hydraulic low-lime calcium silicates such as gamma-C2S, C3S2 and CS were found to achieve a reaction rate close to that of C3S. Fourier transformed infrared (FTIR) spectroscopy and scanning electron microscope (SEM) tests were performed to characterize the carbonation reaction products of the calcium silicate phases. The FTIR spectra during the early stage of carbonation reaction showed formation of calcium silicate hydrate (C-S-H) from C3S, gamma-C2S, beta-C2S, and C3S2 phases with a similar degree of polymerization as that of the C-S-H that forms during the hydration reaction of C3S. However, upon further exposure to CO2, these C-S-H phases decompose and eventually converted to calcium-modified (Ca-modified) silica gel phase with higher degree of silicate polymerization. Contradictorily, CS phase started forming Ca-modified silica gel phase even at the early stage of carbonation reaction. This paper also revealed the stoichiometry of the Ca-modified silica gel that formed during the carbonation reaction of the calcium silicate phases using the SEM/energy dispersive spectroscopy (EDS) and TGA results.