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Case retrieval is the focal stage of Case-Based Reasoning systems whose quality is determined by the speed and accuracy of retrieva1. In this work, we aim at developing a better Case retrieval algorithm by using vector model and propose its new case retrieval Algorithm based on Structure Matrix, wich is derived to learn the kernel matrix for capturing the relations between the case structure units based on matrix iterative analysis. The experimental comparison of similarity shows that using of the structural information of the case, the accuracy of their experimental results has a general increase, when opposed to some of the existing similarity measure. The same learning algorithm based on matrix iteration method compared to other methods, have higher accuracy (5% to 8%), and required less training documents, the computational cost is smaller