In this work, Ag/Bi5O7I nanocomposite was prepared and firstly applied in piezo/photocatalytic reduction of N2 to NH3 and methyl orange (MO) degradation. Bi5O7I was synthesized via a hydrothermal-calcination method and shows nanorods morphology. Ag nanoparticles (NPs) were photo deposited on the Bi5O7I nanorods as electron trappers to improve the spatial separation of charge carriers, which was confirmed via XPS, TEM, and electronic chemical analyses. The catalytic test indicates that Bi5O7I presents the piezoelectric-like behavior, while the loading of Ag NPs can strengthen the character. Under ultrasonic vibration, the optimal Ag/Bi5O7I presents high efficiency in MO degradation. The degradation rate is determined to be 0.033 min−1, which is 4.7 folds faster than that of Bi5O7I. The Ag/Bi5O7I also presents a high performance in piezocatalytic N2 fixation. The piezocatalytic NH3 generation rate reaches 65.4 μmol L−1 g−1 h−1 with water as a hole scavenger. The addition of methanol can hasten the piezoelectric catalytic reaction. Interestingly, when ultrasonic vibration and light irradiation simultaneously act on the Ag/Bi5O7I catalyst, higher performance in NH3 generation and MO degradation is observed. However, due to the weak adhesion of Ag NPs, some Ag NPs would fall off from the Bi5O7I surface under long-term ultrasonic vibration, which would greatly reduce the piezoelectric catalytic performance. This result indicates that a strong binding force is required when preparing the piezoelectric composite catalyst. The current work provides new insights for the development of highly efficient catalysts that can use multiple energies.