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In order to reduce the errors of the reliability of the retaining wall structure in the establishment of function, in the estimation of parameter and algorithm, firstly, two new reliability and stability models of anti-slipping and anti-overturning based on the upper-bound theory of limit analysis were established, and two kinds of failure modes were regarded as a series of systems with multiple correlated failure modes. Then, statistical characteristics of parameters of the retaining wall structure were inferred by maximal entropy principle. At last, the structural reliabilities of single failure mode and multiple failure modes were calculated by Monte Carlo method in MATLAB and the results were compared and analyzed on the sensitivity. It indicates that this method, with a high precision, is not only easy to program and quick in calculation, but also without the limit of nonlinear functions and non-normal random variables. And the results calculated by this method which applies both the limit analysis theory, maximal entropy principle and Monte Carlo method into analyzing the reliability of the retaining wall structures is more scientific, accurate and reliable, in comparison with those calculated by traditional method.