Time of arrival (TOA) is a widely used wireless cellular network ranging technology. How to perform accurate TOA estimation in multi-path and non-line-of-sight (NLOS) environments and then accurately calculating mobile terminal locations are two critical issues in positioning research. NLOS identification can be performed in the TOA measurement part and the position calculation part. In this paper, for the above two steps, two schemes for mitigating NLOS errors are proposed. First, a TOA ranging method based on clustering theory is proposed to solve the problem of line-of-sight (LOS) path estimation in multi-path channels. We model the TOA range as a Gaussian mixture model and illustrate how LOS and NLOS can be measured and identified based on non-parametric Bayesian methods when the wireless transmission environment is unknown. Moreover, for NLOS propagation channels, this paper proposes a user location estimator based on the maximum a posteriori criterion. Combined with the TOA estimation and user location computation scheme proposed in this paper, the terminal's positioning accuracy is improved. Experiments showed that the TOA measurement and localization algorithms presented in this paper have good robustness in complex wireless environments.