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Measurements of residual stress in a printed circuit board, which consists of copper foil, silver alloy and thermo plastic resin, were conducted under a thermal cycle. The printed circuit board was given a ten-layer repeat of prepreg and made by thermocompression bonding. Experiments suggested the possibility of measuring surface residual stress of copper circuits and the internal residual stress of metallic connections by synchrotron radiation of Spring-8. FEM analysis of the printed circuit board during a thermal cycle was conducted, and the result was adjusted to X-ray stress using absorption correction. X-ray stress during a heat-cycle obtained by synchrotron radiation showed good agreement with stress calculated by FEM analysis.