The Wiener model, composed of a linear dynamical block and a nonlinear static one connected in series, is frequently used for prediction in Model Predictive Control (MPC) algorithms. The parallel structure is an extension of the classical Wiener model; it is expected to offer better modeling accuracy and increase the MPC control quality. This work discusses the benefits of using the parallel Wiener model in MPC. It has three objectives. Firstly, it describes a fast MPC algorithm in which parallel Wiener models are used for online prediction. In the presented approach, sophisticated trajectory linearization is performed online, which leads to computationally fast quadratic optimization. The second objective of this work is to study the influence of the model structure on modeling accuracy. The well-known neutralization benchmark process is considered. It is shown that the parallel Wiener models in the open-loop mode generate significantly fewer errors than the classical structure. This work’s third objective is to validate the efficiency of parallel Wiener models in closed-loop MPC. For the neutralization process, it is demonstrated that parallel models demonstrate better control quality using various indicators, but the difference between the classical and parallel models is not significant.