To produce castings of titanium, nickel, copper, aluminum, and zinc alloys, graphite molds can be used, which makes it possible to provide a high cooling rate. No die coating and lubricant are required in this case. Computer simulation of casting into graphite molds requires knowledge of the thermal properties of the poured alloy and graphite. In addition, in order to attain adequate simulation results, a series of boundary conditions such as heat transfer coefficients should be determined. The most important ones are the interface heat transfer coefficient between the casting and the mold, the heat transfer coefficient between the mold parts, and the interface heat transfer coefficient into the environment. In this study, the interface heat transfer coefficient h between the cylindrical aluminum (99.99%) casting and the mold made of block graphite of the GMZ (low ash graphite) grade was determined. The mold was produced by milling using a CNC milling machine. The interface heat transfer coefficient was found by minimizing the error function reflecting the difference between the experimental and simulated temperatures in a mold and in a casting during pouring, solidification, and cooling of the casting. The dependences of the interface heat transfer coefficient between aluminum and graphite on the casting surface temperature and time passed from the beginning of pouring are obtained. It is established that, at temperatures of the metal surface contacting with a mold of 1000, 660, 619, and 190°C, the h is 1100, 4700, 700, and 100 W/(m2 K), respectively; i.e., when cooling the melt from 1000°C (pouring temperature) to 660°C (aluminum melting point), the h rises from 1100 to 4700 W/(m2 K), and after forming the metal solid skin on the mold surface and decreasing its temperature, the h decreases. In our opinion, a decrease in the interface heat transfer coefficient at casting surface temperatures lower than 660°C is associated with the air gap formation between the surfaces of the mold and the casting because of the linear shrinkage of the latter. The heat transfer coefficient between mold parts (graphite–graphite) is constant, being 1000 W/(m2 K). The heat transfer coefficient of graphite into air is 12 W/(m2 K) at a mold surface temperature up to 600°C.