A new x-ray technique to determine temperature dependencies of macroscopic stresses in thin films by characterizing the substrate curvature is introduced. The technique is demonstrated on polycrystalline TiN and Al thin films deposited on Si(100) wafers. The structures are thermally cycled in the temperature range of 25-400 degrees C using a newly developed heating chamber attached to a commercial x-ray diffractometer. The curvature of the freestanding samples was determined by the rocking curve measurement of substrate Si 400 reflections at different lateral positions of the samples, and the stresses are calculated using Stoney's formula. The results show that the magnitude of the stress is in good agreement with the results obtained by other techniques. For the practical application of the technique, the sample mounting and the temperature control are of great importance.