This paper introduces a new approach to controlling Pressure Swing Adsorption (PSA) using a neural network controller based on a Model Predictive Control (MPC) process. We use a Hammerstein–Wiener (HW) model representing the real PSA process data. Then, we design an MPC-controlled model based on the HW model to maintain the bioethanol purity near 99% molar fraction. This work proposes an Artificial Neural Network (ANN) that captures the dynamics of the PSA model controlled by the MPC strategy. Both controllers are validated using the HW model of the PSA process, showing great performance and robustness against disturbances. The results show that we can follow the desired trajectory and attenuate disturbances, achieving the purity of bioethanol at a molar fraction value of 0.99 using the ANN based on the MPC strategy with 94% of fit in the control signal and a 97% fit in the purity signal, so we can conclude that our ANN can be used to attenuate disturbances and maintain purity in the PSA process.