In this study, Fe/TiC composite coating was fabricated on the surface of 65Mn steel using substrate preheating combined with laser cladding technology. In order to characterize the impact of various preheating temperatures, four coatings were fabricated on a 65Mn substrate using laser cladding at different temperatures (ambient temperature, 100 °C, 200 °C, and 300 °C). The microstructures and properties of four Fe/TiC composite coatings were investigated using SEM, XRD, EDS, a Vickers microhardness meter, a wear tester, and an electrochemical workstation. The research results show that the cladding angle of the Fe/TiC composite coating initially increases and then decreases as the substrate preheating temperature rises. The solidification characteristics of the Fe/TiC composite coating structure are not obviously changed at substrate preheating temperatures ranging from room temperature to 300 °C. However, the elemental distribution within the cladding layer was significantly influenced by the preheating temperature. An increase in the preheating temperature led to a more uniform elemental distribution. Regarding the comprehensive properties, including hardness, wear characteristics, and corrosion resistance, the optimum substrate preheating temperature for the cladding layer was found to be 300 °C.