Yb(3+) ions with various site symmetries have been observed in the absorption and emission spectra of Yb(3+):CaF(2) crystals, both γ-irradiated and annealed in hydrogen. The absorption intensity value is found to be much higher for the γ-irradiated crystal and strongly dependent on the gamma dose. The UV absorption spectra of γ-irradiated and H(2)-annealed CaF(2):5 at.% Yb(3+) crystals are quite similar. Yb(2+) absorption bands are observed at 360, 315, 271, 260, 227 and 214 nm, which are called A, B, C, D, F and G bands, respectively. For γ-irradiated CaF(2):30 at.% Yb(3+), an additional band at 234 nm can be seen. It is suggested that only a negligible amount of Yb(3+) ions are converted into Yb(2+) under the γ-irradiation. The presence of Yb(2+) is confirmed by the 565 and 540 nm luminescence under 357 nm excitation. It is also suggested that the excitation in the A, C, D and F absorption bands of Yb(2+) gives rise to photo-ionization of Yb(2+) ions and electrons in the conduction band to form the excited Yb(3+) ions which emit IR Yb(3+) luminescence.The UV absorption and emission spectra obtained for γ-irradiated and H(2)-annealed crystals have different structures. This suggests that different mechanisms are responsible for the creation of Yb(2+) ions. γ-irradiation favours Yb(2+) isolated centres by reduction of Yb(3+) ions located at Ca(2+) lattice sites, whereas annealing in hydrogen favours Yb(2+) centres neighbouring Yb(3+) ions when a Yb(3+) ion pair captures a Compton electron. Also, γ-irradiation does not change the position of Yb(3+) ions converted into Yb(2+) in the CaF(2) lattice. In the case of H(2) annealing, a Yb(3+) ion converted to Yb(2+) is shifted to the Ca(2+) position in the lattice.