The rapid development of the fifth generation mobile communication systems accelerates the implementation of vehicle-to-everything communications. Compared with the other types of vehicular communications, vehicle-to-vehicle (V2V) communications mainly focus on the exchange of driving safety information with neighboring vehicles, which requires ultra-reliable and low-latency communications (URLLCs). However, the frame size is significantly shortened in V2V URLLCs because of the rigorous latency requirements, and thus the overhead is no longer negligible compared with the payload information from the perspective of size. In this paper, we investigate the frame design and resource allocation for an urban V2V URLLC system in which the uplink cellular resources are reused at the underlay mode. Specifically, we first analyze the lower bounds of performance for V2V pairs and cellular users based on the regular pilot scheme and superimposed pilot scheme. Then, we propose a frame design algorithm and a semi-persistent scheduling algorithm to achieve the optimal frame design and resource allocation with the reasonable complexity. Finally, our simulation results show that the proposed frame design and resource allocation scheme can greatly satisfy the URLLC requirements of V2V pairs and guarantee the communication quality of cellular users.