Beacon broadcasting is of great importance in improving road safety and avoiding dangerous situations in vehicular ad hoc networks (VANETs). In order to support emerging vehicular applications such as autonomous driving, the reliability of beacon broadcasting becomes an indispensable issue which is also difficult given the highly dynamic topology and vehicle density. For the territories which are not covered with communication infrastructure, controlling and scheduling in a centralized way may not be applicable. Therefore, vehicle-to-vehicle (V2V) ad hoc communication is promising to address the ubiquitousness coverage concern. In this paper, a distributed network coding-based medium access control protocol (NC-MAC) is proposed to support V2V beacon broadcasting. We combine the preamble-based feedback mechanism, retransmissions, and network coding together to enhance broadcasting reliability. Extensive simulations are given to show the performance gain of NC-MAC protocol compared to the existing 5 G cellular vehicle-to-everything (C-V2X) MAC protocol in a wide range of scenarios including highway and urban vehicle traces generated by simulation of urban mobility (SUMO). The results show that the proposed protocol can improve the communication reliability as well as scalability.