Abstract: Liquid Li metal is a promising nuclear reactor coolant; however, relevant research regarding its heat transfer characteristics remains insufficient. In this study, a steady-state two-dimensional mathematical model is established to describe the heat transfer process of liquid Li in a straight pipe. A numerical analysis is conducted to investigate the effects of inlet velocity, inlet temperature, and wall heat flux on heat transfer in liquid Li. The results indicate the advantage of using liquid Li for improving heat transfer at high inlet temperatures (> 1000 K) compared with using liquid sodium and lead–bismuth eutectic. Considering the mechanism of the outlet radial heat flow model, the ratio of turbulent to molecular diffusion coefficients presents a parabolic distribution along the radius of the pipe. Increasing the inlet velocity, decreasing the inlet temperature, and decreasing the wall heat flux can effectively weaken the dominant role of molecular heat transfer owing to the low Prandtl number of liquid Li. The heat transfer of liquid Li is investigated comprehensively in this study, and the results provide a basis for the practical application of liquid Li as a promising coolant.