For new submarine hot oil pipelines, accurate simulation of preheating is difficult owing to complex transient flow and coupled heat transfer happening. Using quasi-steady equations to simulate preheating is inadequate as the hydraulic transient phenomenon is neglected. Considering this fact, this paper constructs an unsteady flow and heat transfer coupled mathematical model for the preheating process. By combining the double method of characteristics (DMOC) and finite element method (FEM), a numerical methodology is proposed, namely, DMOC-FEM. Its accuracy is validated by field data collected from the Bohai sea, China, showing the mean absolute percentage error (MAPE) of 4.27%. Simulation results demonstrate that the preheating medium mainly warms submarine pipe walls rather than the surrounding subsea mud. Furthermore, during the preheating process, the equivalent overall heat transfer coefficients deduced performs more applicably than the inverse-calculation method in presenting the unsteady propagation of fluid temperature with time and distance. Finally, according to the comparison results of 11 preheating plans, subject to a rated heat power and maximum flow, the preheating parameter at a lower fluid temperature combined with a higher flow rate will produce a better preheating effect.