<p>Piezoelectric materials have been extensively used as energy collector due to their excellent character of environmental vibration energy conversion. However, the existing piezoelectric energy collector model is not suitable for complex multi-layered beam structures. The objective of this paper is to explore the dynamic response and piezoelectric patch energy harvesting of four-layered beams with single unimorph piezoelectric patch subjected to multiple moving loads, and the governing equations are derived by using Hamilton’s principle. The effects of structural lamina parameters and piezoelectric patch parameters of four-layered beams with single piezoelectric patch on dynamic response and optimal energy harvesting are investigated. A detailed parametric analysis of the structural lamina and piezoelectric patch of the four-layered beam model is conducted, and the optimality of energy harvesting parameters of the layered beam is discussed. It is found that the dynamic central deflection of layered beam and output voltage are quite related to the geometrical and physical parameters of each functional layer including the fiber orientation angles. The dynamic central deflection of layered beam is not sensitive to the piezoelectric patch, and so it is suitable of introducing the piezoelectric patch to produce the electric power. The optimum energy harvesting efficiency of the layered beam is also discussed in detail.</p>