Vehicular ad hoc networks can play an important role in enhancing transportation efficiency and improving road safety. Therefore, direct vehicle-to-vehicle communications are considered as one of the main building blocks of a future Intelligent Transportation System. The success and availability of IEEE 802.11 radios made this technology the most probable choice for the medium access control layer in vehicular networks. However, IEEE 802.11 was originally designed in a wireless local area network context and it is not optimised for a dynamic, ad hoc vehicular scenario. In this paper, we investigate the compatibility of the IEEE 802.11 medium access control protocol with the requirements of safety vehicular applications. As the protocols in this family are well-known for their scalability problems, we are especially interested in high density scenarios, quite frequent on today’s roads. Using an analytical framework, we study the performance of the back-off mechanism and the role of the contention window on the control channel of a vehicular network. Based on these findings, we propose a reverse back-off mechanism, specifically designed with road safety applications in mind. Extensive simulations are carried out to prove the efficiency of the proposed enhancement scheme and to better understand the characteristics of vehicular communications.