In today's modern electric vehicles, enhancing the safety-critical cyber-physical system (CPS)'s performance is necessary for the safe maneuverability of the vehicle. As a typical CPS, the braking system is crucial for the vehicle design and safe control. However, precise state estimation of the brake pressure is desired to perform safe driving with a high degree of autonomy. In this paper, a sensorless state estimation technique of the vehicle's brake pressure is developed using a deep-learning approach. A deep neural network (DNN) is structured and trained using deep-learning training techniques, such as, dropout and rectified units. These techniques are utilized to obtain more accurate model for brake pressure state estimation applications. The proposed model is trained using real experimental training data which were collected via conducting real vehicle testing. The vehicle was attached to a chassis dynamometer while the brake pressure data were collected under random driving cycles. Based on these experimental data, the DNN is trained and the performance of the proposed state estimation approach is validated accordingly. The results demonstrate high-accuracy brake pressure state estimation with RMSE of 0.048 MPa.