In situ X-ray diffraction measurement was performed to study the precipitation mechanism of graphene from Ni catalyst with and without Ti capping layer using X-ray beam from a synchrotron radiation facility. The graphene precipitated on the surface of the catalyst in the case without the Ti capping layer while it did at the interface between the catalyst and the sapphire substrate in the case with the Ti capping layer. Each process, such as graphene nucleation and precipitation was successfully monitored even though graphene precipitated under the metal catalyst. The detailed mechanisms for both cases were discussed using the experimental results. Consequently, the crystallization of the catalyst is found to effectively suppress the precipitation at low temperature, which is useful to improve the quality of the precipitated graphene. The adjustment of the amount of the carbons is another important factor to precisely control the precipitation because graphene also precipitates after the carbons saturate the catalyst.