Considering the variety of uncertainties and disturbances in real active vibration control systems, a novel piezoelectric multimode control strategy for an all-clamped stiffened plate (ACSP) structure is proposed in this paper. First, an active disturbance rejection control (ADRC) method, i.e., the extended state observer (ESO)-based vibration control scheme, is employed to ensure the performance of the vibration suppression and rejection of the lumped disturbances of the closed-loop system. Second, a proportional differential controller and an acceleration feedforward controller produce the control law for each vibration mode. Moreover, a chaos optimization method based on a logistic map is introduced to automatically tune the parameters of the feedback channel. The stability and superiority of the proposed controller are theoretically analyzed. Compared with the classical ADRC method, the multimode vibration experimental results demonstrate that the control performance of the first mode is improved from 12.04 to 14.06 dB; meanwhile, the performance of the second mode is also improved, having changed from 11.1 to 13.68 dB.