Thermally induced singular behavior of an arbitrarily oriented crack in a homogeneous substrate overlaid with a functionally graded coating is considered, within the framework of linear plane thermoelasticity. It is assumed that the graded coating/substrate system is subjected to steady-state thermal loading applied over a finite region at the coating surface and the crack in the substrate is thermally insulated, disturbing the prescribed heat flow. Based on the method of Fourier integral transform and the coordinate transformations of basic field variables in thermoelasticity equations, formulation of the crack problem is reduced to two sets of Cauchy-type singular integral equations for temperature and thermal stresses in the coated medium. In the numerical results, the main emphasis is placed on the investigation of influences of loading, geometric, and material parameters of the coated system on the variations of mixed-mode thermal stress intensity factors. Further addressed are the probable cleavage angles for the incipient growth of the original crack and the corresponding values of effective tensile-mode stress intensity factors.