As one of the most promising communication technologies for vehicular networks, LTE-V has the advantages of wide coverage and a high transmission rate. 3GPP released the technical specification of LTE-V in March 2017, launching a spate of related research and industrialization. In this paper, we propose a communication model based on Markov process to evaluate the reliability of LTE-V. We derived the Packet Delivery Rate (PDR) of LTE-V based on the model. Moreover, we use Poisson process to model the distribution of vehicles on a highway, then combine the communication model with the vehicles’ distribution to derive the PDR under this scenario. To verify the correctness of the proposed model, we established a simulation program on the MATLAB platform. By comparing the simulation results and the mathematical results, we found that simulation results are a very good fit for the model.