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In this paper, the Gaussian mixture model (GMM) is introduced to the channel multipath clustering. In the GMM field, the expectation-maximization (EM) algorithm is usually utilized to estimate the model parameters. However, the EM widely converges into local optimization. To address this issue, a hybrid differential evolution (DE) and EM (DE-EM) algorithms are proposed in this paper. To be specific, the DE is employed to initialize the GMM parameters. Then, the parameters are estimated with the EM algorithm. Thanks to the global searching ability of DE, the proposed hybrid DE-EM algorithm is more likely to obtain the global optimization. Simulations demonstrate that our proposed DE-EM clustering algorithm can significantly improve the clustering performance.