Internet of Vehicles (IoV) is an emerging paradigm with significant potential to improve traffic efficiency and driving safety. Here, we focus on the design of a novel visible light communication (VLC)-assisted scheme to enable driving safety-related Internet of Vehicles (IoV) services that require ultrareliable and low-latency communications (URLLC). Specifically, the Vehicle-to-Vehicle (V2V) communication mode is adopted to satisfy the ultralow latency requirement of URLLC in roadside infrastructure-less IoV systems. In the outdoor V2V- VLC scenarios, the quality of the received optical signal is degraded by path loss, atmospheric turbulence and additive noise. In addition, the short-packet feature of URLLC introduces inevitable data decoding errors and imperfect channel state information (CSI). With this background, we aim to investigate the reliability performance of URLLC in outdoor V2V- VLC systems, which is described by the average packet loss probability under given user-plane transmission latency. First, we consider the ideal case of a perfect CSI at the receiver, and derive an analytical expression of average packet loss probability. Further, a closed-form approximation is provided to simplify the numerical calculation. Next, we extend the theoretical analysis to a practical V2V- VLC system with imperfect CSI at the receiver. Through numerical results, we validate the accuracy of our designed theoretical framework and propose ideas to enable driving safety-related IoV services in outdoor V2V- VLC systems.