RFID technologies have attracted a lot of attention in recent years because of their cost/time-effectiveness in large-scale logistics, supply chain management (SCM) and other various potential applications. One of the most important issues of the RFID-based systems is how quickly tags can be identified. Tag collision arbitration plays a more critical role in determining the system performance especially for passive tag-based ones where tag collisions are dealt with rather than prevented. We present a novel tag collision arbitration protocol called Optimum Frame-Slotted Aloha (OFSA). The protocol has been designed to achieve time-optimal efficiency in tag identification through an analytic study of tag identification delay and tag number estimation. Results from our analysis and extensive simulations demonstrate that OFSA outperforms other collision arbitration protocols. Also, unlike most prior anti-collision protocols, it does not require any modification to the current standards and architectures facilitating the rollout of RFID systems.