The traditional effective variance weighted least squares algorithms for solving CMB (Chemical Mass Balance) models have the following drawbacks: When there is collinearity among the sources or the number of species is less than the number of sources, then some negative value of contribution will appear in the results of the source apportionment or the algorithm does not converge to calculation. In this paper, a novel robust algorithm based on enhanced sampling Monte Carlo simulation and effective variance weighted least squares (ESMC-CMB) is proposed, which overcomes the above weaknesses. In the following practical instances for source apportionment, when nine species and nine sources, with no collinearity among them, are selected, EPA-CMB8.2 (U.S. Environmental Protection Agency-CMB8.2), NKCMB1.0 (NanKai University, China-CMB1.0) and ESMC-CMB can obtain similar results. When the source raise dust is added to the source profiles, or nine sources and eight species are selected, EPA-CMB8.2 and NKCMB1.0 cannot solve the model, but the proposed ESMC-CMB algorithm can achieve satisfactory results that fully verify the robustness and effectiveness of ESMC-CMB.