In this paper, a new model free adaptive control method based on self-adjusting PID Algorithm (MFAC-SA-PID) is proposed to solve the problem that the pH process with strong nonlinearity is difficult to control near the neutralization point. The MFAC-SA-PID method also solves the problem that the parameters of the model free adaptive control (MFAC) method are not easy to be adjusted and the effect is not obvious by introducing a fuzzy self-adjusting algorithm to adjust the controller parameters. Then the convergence and stability of the MFAC-SA-PID method are proved in this paper. In the simulation study, the control performance of the MFAC-SA-PID method proposed in this paper is compared with the traditional MFAC method and the improved model free adaptive control (IMFAC) method, respectively. The results show that the proposed MFAC-SA-PID method has better control effect on the pH neutralization process. The MFAC-SA-PID control performance also outperforms the traditional MFAC method and IMFAC method when step input disturbances are added, which indicates that the MFAC-SA-PID method has better robustness and stability.