The coupling nature of piezoelectric materials has acquired wide applications in electric-mechanical and electric devices. Recent advances in smart structures technology have led to a resurgence of interest in piezoelectricity, and in particular, in the solution of fundamental boundary value problems. In this paper, an analytic solution to the axisymmetric problem of a radially polarized, radially orthotropic piezoelectric hollow cylinder with thermal gradient is developed. An analytic solution to the governing equilibrium equations (a coupled system of second-order ordinary differential equations) is obtained. On application of the boundary conditions, the problem is reduced to solving a system of linear algebraic equations. The stress and potential field distributions in the cylinder are obtained numerically for two piezoceramics. It is shown that the hoop stresses in a cylinder composed of these materials can be decreased throughout the cross-section by applying an appropriate set of boundary conditions.