CdTe:Bi crystals were grown by the vertical Bridgman method, varying the nominal Bi-dopant concentration in the range of 1 x 10(17) -1 x 10(19) at/cm(3). Bi and Bi1.8-2.3Te precipitates are the most characteristic structural defects in these crystals. Raman spectroscopy studies have shown that Bi traps Te from the CdTe host lattice. Low-temperature photoluminescence in the 1.2-1.6eV energy region is presented. Several new emissions related to the incorporation of Bi are observed. Semi-insulating CdTe was obtained (rho = 2 x 10(10) Omega cm) for dopant concentration of the order of 1 x 10(17) at/cm(3). The resisitivity decreased to values as lower as 1 x 10(5) Omega cm for higher concentrations. Photosensitivity studies show an evolution from typical conductivity to shallow acceptor defects-related conduction when the Bi concentration is increased. (c) 2006 Elsevier B.V. All rights reserved.