A high-quality Cr3+:CdWO4 single crystal at a size of approximately \Phi 25 \times 80 mm is grown using the Bridgman method with CdO, WO3, and Cr2O3 as raw materials and their molar ratio of 100:100:0.5. The temperature gradient of solid-liquid interface at growth is approximately 50 oC/cm and the growth rate is 0.05 mm/h. The X-ray diffraction (XRD), absorption, excitation, and emission spectra of different parts of the as-grown and O2-annealed crystals are investigated. Two strong broad optical absorption bands of about 472 and 708 nm are observed, and they are associated with the transitions 4A2->4T1 and 4A2->4T2. The weak 4T2->2E transition (the R-line) at 632 nm is also observed. The crystal-field parameter Dq and the Racah parameters B and C are estimated to be 1 412.4, 776.8, and 3 427.6 cm-1, respectively, according to the absorption spectra and crystal-splitting theory. A broadband fluorescence at about 1 000 nm due to 4T2->4A2 transition is produced by exciting the samples at 675 nm. After being annealed in an O2 atmosphere, the crystals become more transparent, while the effective light absorption of Cr3+ ions is evidently enhanced and the emission intensity is also strengthened due to the reduction of oxygen vacancies in the CdWO4 crystal after annealing.