A novel scheme to optimize the adaptive transmit waveform of chaotic multiple-input multiple-output (MIMO) radar is developed. The main objective of this work is to achieve high ability in target discrimination by using a Dirichlet process mixture model (DPMM)-based clustering method based on nonparametric Bayesian theory and to improve the capability of target detection by minimizing the mean square error of radar channel response via Kalman filtering (KF) technique. The two stages are the discrimination of multiple range-extended targets and the optimization of the adaptive chaos-based waveform for transmission. The adaptive chaotic MIMO waveform optimization scheme overcomes the problem of target discrimination and detection in an intelligent transportation system, where there is a need for extracting the feature of target information achieved from vehicle-mounted sensor. As the number of iterations increases, simulation experiments demonstrate better target discrimination capability provided by the proposed DPMM-KF technique as compared with the traditional waveform design method. In addition, the proposed DPMM-KF technique leads to improved target detection probability and receiver operating characteristics in the interference environment.