The amorphous GeO2 is generated with the 'melt-and-quench' technique, and molecular dynamics simulations are performed to investigate the structural changes from 1 GPa up to 25 GPa. The five- and six-coordinated Ge-O arrangements increase during the pressurized process. The structure is observed to experience compression inside the tetrahedra under the pressure below 5 GPa. The structural transition from tetrahedral to pentahedral dominant structure takes place during 13-15 GPa. The interstitial radius distribution, void size distribution without overlaps, and the bottleneck radius distribution are shown to decrease with the densification of the system. The largest void channels decrease their radii from 3.9 angstrom at 1 GPa to 1.2 angstrom at 25 GPa. Crown Copyright (C) 2009 Published by Elsevier B. V. All rights reserved.