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The structure of the algebraic system which results from the use of Haar wavelet when solving Poisson’s equation is studied. Haar wavelet technique is used to solve Poisson’s equation on a unit square domain. The form of collocation points are used at the mid points of the subintervals i.e at the odd multiple of the sub interval length labeling. It is proved that the coefficient matrix has symmetric block structure. Comparison with the tridagonal block structure obtained by the finite difference with the natural ordering is introduced. The numerical results have illustrated the superiority of the use of Haar wavelet technique. The matrices obtained can be used for any equations containing the Laplace operator.