Under ArF laser (193 nm) the main luminescence is yellow–red in P-doped α-quartz crystal. It is observed both in γ- irradiated and in annealed at 700 K samples even intensity of PL is higher in annealed samples. At 293 K it is broad complex band with a shoulder in red part of spectra, Fig. 8. This red band excited with KrF laser (248 nm) is presented Fig. 9. Its intensity grows with cooling to 9 K in fashion presented in inset of Fig. 9. The decay curves are well approximated with exponents with time constant about 4 ms at 9 K, when excitation was done by KrF laser.