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A complex investigation of the dynamics of electronic excitations in potassium dihydrophosphate (KDP) crystals is performed by the low-temperature time-resolved vacuum ultraviolet optical luminescence spectroscopy with subnanosecond time resolution and with selective photoexcitation by synchrotron radiation. For KDP crystals, data on the kinetics of the photoluminescence (PL) decay, time-resolved PL spectra (2–6.2 eV), and time-resolved excitation PL spectra (4–24 eV) at 10 K were obtained for the first time. The intrinsic character of the PL of KDP in the vicinity of 5.2 eV, which is caused by the radiative annihilation of self-trapped excitons (STEs), is ascertained; σ and π bands in the luminescence spectra of the STEs, which are due to singlet and triplet radiative transitions, are resolved; and the shift of the σ band with respect to the π band in the spectra of the STEs is explained. [Copyright &y& Elsevier]