The performance of CdZnTe X/γ-ray detectors is strongly affected by the electric field distribution in terms of charge transport and charge collection. Factors which determine the electric field distribution are not only electric contact, but also intrinsic defects, especially grown-in twin boundaries. Here, the electric field distribution around twin boundaries is investigated in a CdZnTe bicrystal detector with a {111}–{111} twin plane using the Pockels electro-optic effect. The results of laser beam induced current pulses are also obtained by the transient current technique, and we discuss the influence of the twin boundary on the electric field evolution. These studies reveal a significant distortion of the electric field, which is attributed to the buildup of space charges at twin boundaries. Also, the position of these space charge regions depends on the polarity of the detector bias. An energy band model based on the formation of an n–n+–n junction across the twin boundary has been established to explain the observed results.