This paper presents a method for online identification of non-linear dynamic systems using the Wiener model. For the linear dynamic part the subspace identification method with the multivariable output-error state-space algorithm is employed, whereas for the non-linear static part the multi-layer perceptron neural network with Levenberg–Marquardt algorithm is used. The stability and convergence of the proposed method is shown using the Lyapunov direct method and the region solution of the linear matrix inequality (LMI) approach. The proposed method is tested by simulations performed on the continuous stirred tank reactor (CSTR) plant, which is presented by non-linear differential equations. Moreover, the method is applied on the input–output data that are obtained from a practical system of the CSTR plant as well as the pH neutralization plant. The results show significant improvements in online identification of the non-linear dynamic systems compared with the recently reported methods in literature.