The large relative error between the measurements and the fitted values with the least squares method easily occurred when the small outputs of CCD. According to this problem, the evaluation method with minimizing the value of the maximum relative error was proposed to solve the optimum curve fitting with the neural dynamic optimization algorithm. Firstly, the CCD opto-electronic responses were achieved by using the high power LED as a linear light source, and the polynomial fitting error model was advanced. Then the neural dynamic optimization algorithm was used to solve it. The experimental results show that the optimum algorithm is stable and effective, and the maximum relative error is not more than 2.5% in the third order polynomial fitting with the neural dynamics. The relative error is obviously reduced in comparison with the least square method. By analyzing the responses, the CCD ICX694AL is with linear characteristics in the unsaturated region. However, it has obvious nonlinear effects in the saturated region.