In recent years, the Vehicle-to-Vehicle (V2V) communication system has been considered one of the most promising technologies to build a much safer and more efficient transportation system. Both simulation and field test have been extensively performed to evaluate the performance of the V2V communication system. However, most of the evaluation methods are communication-based, and although in a transportation environment, lack a V2V application-oriented analysis. In this study, we conducted real-world tests and built an application-oriented evaluation model. The experiments were classified into four scenarios: static, following, face 2 face, and crossing vertically, which almost covered all the V2V communication patterns on the road. Under these scenarios, we conducted experiments and built a probability model to evaluate the performance of 802.11p and LTE-V in safety-related applications. Consequently, we found out that improvements are still needed in Non-Line-of-Sight scenarios.