Based on the superiority avoiding the matrix equation to be morbid for those fitting functions constructed by orthogonal base, the Legendre orthogonal polynomial is adopted to fit the experimental data of concrete uniaxial compression stress-strain curves under the frame of least-square . With the help of FORTRAN programming, 3 series of experimental data is fitted. And the fitting effect is very satisfactory when the item number of orthogonal base is not less than 5. What’s more, compared with those piecewise fitting functions, the Legendre orthogonal polynomial fitting function obtained can be introduced into the nonlinear harden-soften character of concrete constitute law more convenient because of its uniform function form and continuous derived feature. And the fitting idea by orthogonal base function will provide a widely road for studying the constitute law of concrete material.