High-energy X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR) of amorphous solid water (ASW) were studied during vapor deposition and the heating process. From the diffraction patterns, the oxygen-oxygen pair distribution functions (PDFs) were calculated up to the eighth coordination shell and an r = 23 Å. The PDF of ASW obtained both during vapor deposition at 80 K as well as the subsequent heating are consistent with that of low-density amorphous ice. The formation and temperature-induced collapse of micropores were observed in the XRD data and in the FTIR measurements, more specifically, in the OH stretch and the dangling mode. Above 140 K, ASW crystallizes into a stacking disordered ice, Isd. It is observed that the fourth, fifth, and sixth peaks in the PDF, corresponding to structural arrangements between 8 and 12 Å, are the most sensitive to the onset of crystallization.