The nonlinear behaviors and energy harvesting of an unsymmetric cross-ply square composite laminated plate with a piezoelectric patch is presented. The unsymmetric cross-ply square composite laminated plate has two stable equilibrium positions by applying thermal stress, thus having snap-through with larger amplitude between the two stable equilibrium positions relative to the general laminated plate. Based on the von-Karman large deformation theory, the nonlinear electromechanical coupling equations of motion of the unsymmetric composite laminated plate with a piezoelectric patch are derived by using Hamilton’s principle. The influence of the base excitation amplitude on nonlinear behaviors and energy harvesting are investigated. For different base excitation amplitudes, the motions of the system demonstrate periodic motion, quasi-periodic motion, chaotic motion and snap-through, and two single-well chaotic attractors and a two-well chaos attractor coexist. Moreover, the power generation efficiency is optimal when the excitation amplitude is in a certain range due to its own unique nonlinear characteristics. The unsymmetric cross-ply square composite laminated plate subjected to thermal stress can actually be called a kind of bistable composite shell structure that has a broad application prospect in combination with morphing aircraft, large deployable antenna and solar panel, which are very likely to have nonlinear vibration.