The cross-well dynamic of the bi-stable laminates triggered by ambient vibration is a typical nonlinear dynamic, the larger deformation makes the bi-stable laminates attract much attention in vibration energy harvesting. To obtain the performance of cross-well dynamics and vibration energy harvesting of the bi-stable laminate theoretically, a 4-layer harmonic base-excited antisymmetric cross-ply bi-stable laminates with d31 type Marco fiber composite (MFC) for vibration energy harvesting is proposed. The bi-stable laminate is fixed at a chosen point where a base excitation is applied as displacement excitation. The first order shear deformation laminated plate theory (FSDT), geometric nonlinear, and the energy principle are employed to obtain the governing equation of the system in terms of the polynomial coefficients of configuration functions. Two stable configurations are calculated by the principle of minimum potential energy, which is used as the initial state for the energy harvesting analysis. The stable configurations are predicted, and evaluated by comparing them with ABAQUS. The cross-well nonlinear dynamic behaviors and the performance of energy harvesting are analyzed. The effects of excitation level, excitation frequency, and the position of the fixed point on the cross-well dynamics and energy harvest characteristics of the antisymmetric bi-stable laminates are investigated in-depth, and some new aspects are revealed. It demonstrates that the base displacement harmonic excitation can induce chaotic cross-well vibration in a high-frequency band when the fixed point is far away from the center point, the various cross-well vibration of the system is more likely to occur in the dominate-frequency resonant band.