In ZnTe:V bulk crystals with nominal vanadium concentrations between 1000 and 7000 ppm three vanadium-ion states V ϩ , V 2ϩ , and V 3ϩ were found in low-temperature optical measurements. No-phonon lines of the internal emissions were detected for the 5 E(D)→ 5 T 2 (D) transition of V ϩ ͑d 4 ͒ at 3401 cm Ϫ1 ͑0.422 eV͒, for 4 T 2 (F)→ 4 T 1 (F) of V 2ϩ ͑d 3 ͒ at 4056 cm Ϫ1 ͑0.503 eV͒, and for 3 T 2 (F)→ 3 A 2 (F) of V 3ϩ ͑d 2 ͒ at 4726 cm Ϫ1 ͑0.586 eV͒. The energies of the internal transitions are reduced with respect to the corresponding transitions in ZnS:V and ZnSe:V. The respective excitation spectra display, in addition to broad charge-transfer bands, higher excited levels of the individual charge states. Crystal-field calculations of the detected transition energies based on the Tanabe-Sugano scheme are presented. With the help of sensitization experiments, a one-electron model is designed, in which the donor level ͑V 2ϩ /V 3ϩ ͒ is situated 12 500 cm Ϫ1 ͑1.55 eV͒ below the conduction-band edge and the acceptor level ͑V 2ϩ /V ϩ ͒ 9400 cm Ϫ1 ͑1.17 eV͒ above the valence-band edge. The dynamical behavior of the three infrared luminescence bands was measured. Decay time constants of 43 s ͑V ϩ ͒, 120 s ͑V 2ϩ ͒, and 420 s ͑V 3ϩ ͒ were found. Electron-paramagnetic-resonance ͑EPR͒ results measured on the same samples are presented in an accompanying paper and confirm the optical detection of isolated substitutional V 2ϩ ͑d 3 ͒ and V 3ϩ ͑d 2 ͒ ions. Relations between the EPR and optical results are discussed.