In this paper, an effective multiuser detection (MUD) is proposed for direct sequence ultrawideband-(DS-UWB-) based space formation flying systems. e proposed method called GMM-MUD is based on Gaussian mixture models (GMMs) to suppress multiple access interference. e GMM describes probability distributions of the hypothesis testing problem which is used for bit classification. To reveal the difference between correct bits and error bits, the preprocessing operation applies a mapping function based on optimal multiuser detection. e parameters of GMM are estimated by using expectation-maximization (EM) algorithm. EM algorithm employs iterative operation to simplify the complexity of maximum likelihood estimation method and considers the mapping values of received bits as the observations. Simulation results demonstrate that the proposed GMM-MUD algorithm achieves good performances in terms of bit error rate performance, user capacity, and near-far resistance. Moreover, the computational complexity is low enough for space formation flying applications.