The effect of the incorporation of Bi in the structure of Cd1-xZnxTe bulk crystals has been investigated by ion channeling, X-ray and neutron diffraction techniques. The analysis of the data reveals that the growing method produces high quality crystals, which are uniformly degraded by the incorporation of Bi. Bismuth shows an amphoteric behavior with the ability to occupy Te positions in the zinc-blende structure and it has been found that Bi also goes to a new site (1/4 1/4 5/4). These results explain the important properties of the material and pave the way for enhanced X-and gamma-rays room temperature detectors. Crown Copyright (C) 2009 Published by Elsevier B. V. All rights reserved.