With the large-scale adoption of electric vehicles (EVs) on expressways, the exploration of a guiding-based charging method to effectively adjust interactions between EVs and the fast charging stations (CSs) is urgently needed. This paper proposes a status-of-use (SOU) price-based charging strategy that can motivate users to charge in advance. A queuing model for a CS cluster was established to verify the effectiveness of the strategy, and then a simulation of traveling and charging conditions of 12,000 pure EVs on the road network from 0:00 to 24:00 was performed according to the related data and using the Monte Carlo method, the Floyd-Warshall algorithm, and the queuing algorithm proposed in this paper. Compared to unordered charging (UC), SOU price-based charging can not only reduce the charging cost and waiting time for users, but also increase the utilization ratio of charging facilities in a CS cluster and thus lower their influence on the power grid and expressway traffic. SOU price-based charging can effectively adjust interactions between EVs and CSs.