This letter presents an innovative single-site angle of arrival (AOA) and time difference of arrival (TDOA) hybrid localization algorithm for non-line-of-sight (NLOS) scenarios. An advanced ray-tracing (RT) method is employed to evaluate channel propagation in complex environments, transforming NLOS paths between the base station (BS) and mobile station (MS) into equivalent LOS paths by leveraging multipath propagation. This process identifies generalized sources (GSs) in the BS's environment, including LOS, reflective, diffractive, and transmissive sources. A novel weighting algorithm based on an assignment optimization approach is proposed to determine the locations of TDOA reference stations and assign weights to the TDOA/AOA hybrid equations. Furthermore, considering the significant NLOS noise in the hybrid TDOA/AOA equations, the proposed method integrates a weighting-enhanced iterative reweighted least squares (W-IRLS) algorithm to enhance the robustness of the localization process. Simulation results demonstrate that the proposed algorithm achieves Cramer-Rao lower bound (CRLB)-level accuracy under severe NLOS multipath conditions.