This study examined the possibility of using Pathfinder network analysis to assess Ancient History of China knowledge structures of junior high school students. The results showed:(1)Ancient History of China knowledge structures of high achievement students are closer to a teacher’s referent structure than those of low achievement students.(2)The three indices of similarity discriminate subjects with different achievement group effectively and the PFC Index has the best effect among them.(3)The three indices of similarity predict history academic performances of subjects effectively and the PFC Index still has the best effect among them.(4)The knowledge structure of a teacher is well-organized and that of a low achievement student is ill-organized.