A hybrid‐mixed exact geometry four‐node thermopiezoelectric solid‐shell element through the sampling surfaces (SaS) formulation is proposed. The SaS formulation is based on the choice of an arbitrary number of SaS within layers parallel to the middle surface and located at Chebyshev polynomial nodes in order to introduce the temperatures, displacements and electric potentials of these surfaces as basic shell unknowns. Due to the variational formulation, the outer surfaces and interfaces are also included into a set of SaS. Such choice of unknowns with the use of Lagrange polynomials in the through‐thickness approximations of temperatures, temperature gradient, displacements, strains, electric potential, and electric field leads to a very compact higher‐order thermopiezoelectric shell formulation. To implement efficient analytical integration throughout the solid‐shell element, the extended assumed natural strain method is employed for all components of the temperature gradient, strain tensor, and electric field vector. The developed hybrid‐mixed four‐node thermopiezoelectric solid‐shell element is based on the Hu–Washizu variational principle and shows a superior performance in the case of coarse meshes. It can be useful for the three‐dimensional thermoelectroelastic analysis of thick and thin doubly curved laminated piezoelectric shells under thermal loading, since the SaS formulation allows one to obtain the numerical solutions with a prescribed accuracy, which asymptotically approach exact solutions of the theory of thermopiezoelectricity as a number of SaS tends to infinity.