It is well known that the accident of vehicles carrying hazardous materials incurs huge losses economically and socially. To detect and respond rapidly against the accident of a vehicle carrying hazardous materials, it is essential to estimate the relative navigation information between the forward tractor module and the backward trailer module of the vehicle reliably and accurately. In this paper, a precise relative positioning system based on GPS is designed, implemented, and evaluated as a prerequisite to design an effective relative navigation system for the vehicle carrying hazardous materials. An experiment using field-collected 10 Hz real GPS measurements showed that the designed relative positioning system achieves 22 cm accuracy within 15 epochs by float solutions. Also, it was found that cm-level integer solutions can be generated reliably after the quick convergence of float solutions.