This investigation aims to analyze the effect of homogenization heat treatment at 1240 °C for 2 and 6 h on the hardness, distribution, morphology, and chemical composition of the δ-ferrite and sigma phases in 316L stainless steel cast billet. A field emission scanning electron microscope, combined with electron back-scattered diffraction, a field emission electron probe microanalyzer with a wavelength dispersive spectrometer, and a Vickers microhardness tester are applied to identify various phase evolutions in the cast billet. The morphology of the δ-ferrite and sigma phases in the austenite matrix of the 316L cast billet are strongly related to the subsequent hot and cold wire drawings. The homogenization heat treatment is expected to provide a driving force to form spheroid interdendritic δ-ferrite and to minimize the amount of the brittle sigma intermetallic compound in the austenite matrix. The homogenization heat treatment at 1240 °C effectively spheroidized all δ-ferrites into blunt ones in the cast billet. The transformation of δ-ferrite into sigma is dominated by temperature and cooling rate. The fast air cooling after homogenization between 1240 and 850 °C retards the precipitation of the sigma in the δ-ferrite. There are two δ-ferrite transformation mechanisms in this experiment. The direct transformation of the δ-ferrite into sigma is observed in the as-cast 316L stainless steel billet. In contrast, the eutectoid transformation of the δ-ferrite into the sigma and austenite dominates the 316L cast billet homogenized at 1240 °C, with a slow furnace cooling rate.