The influence of high-pressure hydrogen on the chemical structure of organic materials is essential for designing suitable materials for the safe and efficient use of hydrogen. In this paper, we clarify the cause and mechanism of "explosive failure by decompression" (XDF) in rubber used under high-pressure hydrogen circumstances, and the chemical structure of acrylonitrile butadiene rubber (NBR), which is commonly used for O-rings, was analyzed after exposure to hydrogen at 100 MPa. Solid-state nuclear magnetic resonance (NMR) and liquid-phase NMR for H-1 and C-13, as well as infrared and Raman spectroscopy, were employed for the evaluation. The results show no evidence of structural changes in NBR such as hydrogenation of the olefinic bonds in butadiene or of the cyano groups in acrylonitrile. Copyright (C) 2012, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.