The solidification process of Ni-based superalloy K465 was examined using DTA and X-ray diffraction. The impact of melt structure on solidification process and the morphology of MC carbide and γ′-phase was analyzed. It was observed that an increase in melt peak temperature led to a significant decrease in precipitation temperature for carbides, but only a slight increase in the formation temperature of matrix and eutectic microstructure. The X-ray diffraction results showed that some ordered structures were detected in the sample with melt peak temperature of 1450 °C and 1500 °C, but not in the sample with melt peak temperature of 1360 °C. Furthermore, the ordered structure displayed similar crystalline features with M6C carbide. As the melt peak temperature increased, the carbides changed from block type to script type morphology. This phenomenon was likely caused by the formation of ordered structures at high temperatures. However, the microstructure of γ matrix and γ′ precipitates remained unaffected by the melt peak temperature.