The incorporation and activation of arsenic from tris(dimethylamino)arsine in CdTe layers grown by metal-organic chemical vapor deposition from dimethylcadmium and diisopropyltellurium on GaAs substrates are investigated. The incorporation of arsenic into CdTe depends on the crystallographic orientation of the layers and increases in the series (111)B → (100) → (310). The arsenic concentration in the CdTe layers is proportional to the tris(dimethylamino)arsine flow rate at a power of 1.4 and increases with decreasing diisopropyltellurium/dimethylcadmium ratio from 1.4 to 0.5. After deposition, the CdTe:As layers have p-type conductivity with an arsenic concentration of 1 × 1017–7 × 1018 cm–3 and a hole concentration of 2.7 × 1014–4.6 × 1015 cm–3, respectively; the fraction of electrically active arsenic does not exceed ~0.3%. After annealing in argon (250–450°C), the highest hole concentration is 1 × 1017 cm–3, and the arsenic activation efficiency is ~4.5%. The ionization energy of arsenic determined from the temperature dependence of the hole concentration is in the range of 98–124 meV. The low-temperature photoluminescence spectra of the layers have an emission peak with an energy of ~1.51 eV, which can be attributed to donor–acceptor recombination, where AsTe is an acceptor with an ionization energy of ~90 meV.