We have developed the structure and optical property coincident measurement system equipped with the photo-absorption system to the Large Debye-Scherrer Camera at BL44B2 of the SPring-8. Both photo-absorption detecting systems, the Si pin-photo diode for a 532 nm CW laser and the absorption spectrum covered the range of UV-IR (200∼1400 nm) for a white beam, are adopted. In order to verify the coincident measurement system, the X-ray powder diffraction and photo-absorption with the cyanide complex were performed individually and simultaneously under the temperature changes. As a result, the coincident measurement system performed successfully the one-to-one corresponding measurement between X-ray diffraction and photo-absorption. In addition, the monitoring of the photo-absorption informed us the property change of the material for the measurement condition and the sample transformation by temperature, laser etc. as well as damage by high-brilliance synchrotron radiation X-ray beam.