Large-volume cadmium zinc telluride (CZT) radiation detectors would greatly improve radiation detection capabilities and, therefore, attract extensive scientific and commercial interests. CZT crystals with volumes as large as hundreds of centimeters can be achieved today due to improvements in the crystal growth technology. However, the poor performance of large-volume CZT detectors is still a challenging problem affecting the commercialization of CZT detectors and imaging arrays. We have employed Pockels effect measurements and synchrotron X-ray mapping techniques to investigate the performance-limiting factors for large-volume CZT detectors. Experimental results with the above characterization methods reveal the non-uniform distribution of internal electric field of large-volume CZT detectors, which help us to better understand the responsible mechanism for the insufficient carrier collection in large-volume CZT detectors.