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Structural approach introduced by Goldsmith in 1991 is an integrated method to assess knowledge structure. It includes knowledge elicitation, knowledge representation and evaluation of knowledge representation. On the other hand, a concept map is another method for knowledge representation. Such method has several useful features which are adopted widely in teaching, learning and assessment of mental knowledge. The method in this paper is to assess users' mental knowledge based on structural approach and the helpful features of concept map. A concept map-like representation is generated as an expression of knowledge structure. The representation is used to assess mental knowledge of users according to concept map's characteristics. Therefore, the similarities and dissimilarities of users' mental knowledge can be visualized significantly with this approach.