Structural development of BPDA-PPD polyimide thin film has been investigated by in situ grazing incidence X-ray diffraction at the BL24XU beamline of the SPring-8. Optimizing the sample shape, two-dimensional images were measured successfully without sacrificing angle resolution. It has been clearly shown that the crystallization first begins in the in-plane direction, at the curing temperature of 180 °C, in which the periodic structure of the molecular chain axis (c axis) is developed. The crystallization in the surface normal (out-of-plane) direction is observed later, at the curing temperature above 300 °C. A slight increase of the d spacing of the c axis during heating process has been observed, suggesting the stretching of the contracted molecular chain in accordance with the curing process. In the cooling process, the decrease of the d spacings for a and b axes was considerable, which indicates thermal expansion of the crystals at high temperatures. The increases in the peak intensities during the cooling process have been observed, which indicate the d spacing of each axis becomes close to the equilibrium value to produce higher periodicity.