In this article, the thermoelastic stability behavior of curvilinear fiber‐reinforced composite laminates is investigated using a shear flexible plate theory. The laminate is composed of layers that make use of curvilinear fibers to create spatial variation of stiffness due to the continuous change of fiber orientation within the lamina. Such composite laminates, subjected to different thermal loads like uniform and non‐uniform temperature distributions, are considered in this analysis. The governing equations obtained using the principle of minimization of total potential energy, are solved for evaluating the critical buckling temperature. The displacement fields of pre‐buckling of the laminate are evaluated before proceeding for the thermal buckling analysis. The formulation is checked against available solutions in the literature. A detailed parametric study considering important design parameters such as curvilinear fiber angles, lay‐up, thickness ratio, coefficients of thermal expansion, and modular ratio on the thermoelastic stability/buckling behavior of composite laminates is made. The present analysis highlights the substantial change in the critical buckling loads due to the curvilinear fiber angles, lay‐up and boundary conditions. The new results presented here for curvilinear fiber‐reinforced composite laminate with clamped/mixed boundary conditions may be useful in assessing similar studies based on higher‐order theories or other numerical studies. POLYM. COMPOS., 40:2876–2890, 2019. © 2018 Society of Plastics Engineers