<p>This paper established a model of double-layer rectangular piezoelectric nano-laminated plates with different surface properties on both sides. Taking into account the flexoelectric and surface effects, the buckling behavior of piezoelectric nano-laminated plates was calculated and analyzed. Based on the surface piezoelectric model and flexoelectric theory, the governing equations of piezoelectric nano-laminated plates under the Kirchhoff plate theory were derived using the Hamilton principle, and the solutions for the buckling critical potential and buckling critical load of the piezoelectric nano-laminated plates were obtained. The results show that the influence of the surface effect on the critical electric potential and critical load for the buckling of piezoelectric nano-laminated plates increases as the aspect ratio of the piezoelectric nano-laminated plates increases. The surface effect can increase the critical electric potential and critical load for the buckling of the nano-laminated plates. When the surface residual stress of the nano-laminated plates is negative, the surface effect reduces the critical electric potential and critical load for the buckling of the nano-laminated plates. When the surface residual stress of the nano-laminated plates is positive, the opposite is true, and the influence of the surface effect increases with the increase of the surface residual stress value. The influence of the flexoelectric effect on the critical electric potential and critical load of the buckling of nano-laminated plates will increase as the flexoelectric coefficient of the lower layer plate decreases. Moreover, the flexoelectric effect can increase the critical electric potential and critical load of the buckling of the nano-laminated plates. The research methods and results of this work can provide a theoretical model and analysis method for the microstructure design, multi-physics field characterization and buckling behavior of piezoelectric nano-laminated intelligent elements.</p>