The microstructure is an important factor determining the mechanical properties of A356 alloy. In this experiment, the refiner Al-5Ti-0.6C-1.0Ce master alloys under different preparation temperatures were prepared, and the A356 alloy was refined. The effects of preparation temperature on the number and morphological distribution of each phase in Al-Ti-C-Ce master alloy and the effects of Al-Ti-C-Ce master alloy at different preparation temperatures on the microstructure and mechanical properties of A356 alloy were explored successively. Results showed that, as preparation temperature increased from 850 to 1150 °C, TiAl3 changed from large blocks to long strips and a needle-like phase, and Ti2Al20Ce changed from a bright white block to a broken small block phase. Al-5Ti-0.6C-1.0Ce prepared at 1050 °C can significantly refine the α-Al of A356 alloy and modify eutectic Si. The α-Al grain size was refined from about 1540 to 179.7 μm, and the eutectic Si length was refined from about 22.3 to 17.8 μm with the transition from a coarse needle-like to a short rod-like structure. The ultimate tensile strength and elongation of A356 alloy changed non-monotonically, and the peak values were 282.216 MPa and 3.9% with the Al-Ti-C-Ce preparation temperature of 1050 °C and 950 °C, respectively.