In order to improve the accuracy and reliability of wireless location in NLOS environment, a wireless location algorithm based on artificial neural network (ANN) is proposed for NLOS positioning error caused by non-line-of-sight (NLOS) propagation, such as occlusion and signal reflection. The mapping relationship between TOA and TDOA measurement data and coordinates is established. The connection weights of neural network are estimated as the state variables of nonlinear dynamic system. The multilayer perceptron network is trained by the real-time neural network training algorithm based on extended Kalman (EKF). Combined with the statistical characteristics of NLOS error, the state component NLOS bias estimation is modified to realize TDOA data reconstruction. Simulation and experimental data analysis show that the algorithm can effectively weaken the influence of NLOS error. The localization method does not depend on the specific NLOS error distribution, nor does it need LOS and NLOS recognition. It can significantly improve the mobile positioning accuracy.