There are numerous applications of graph theory and algebraic graph theory in combinatorial optimization and optimal structural analysis. In this paper, a new canonical form as well as its relation with four structural models often encountered in practice and their corresponding graphs are presented. Furthermore, the block diagonalization of this form, which is performed using three Kronecker products and unsymmetric matrices, is studied. This block diagonalization leads to an efficient method for the eigensolution of adjacency and Laplacian matrices of special graphs. The eigenvalues and eigenvectors are used for efficient nodal ordering and partitioning of large structural models. The present method is far more simple than any existing general approach.