New composite scintillation detectors were obtained by incorporation of PPO and o-POPOP organic scintillators into porous sol–gel silica matrices. Composites possess high photoluminescence intensity and decay time in nanosecond range. The absolute light yield of composite scintillators at excitation by alpha-radiation is about 4000–5000 photons/MeV and the pulse–height resolution is about 30%. The investigations of time-resolved luminescence of composites performed under excitation by synchrotron radiation in the 3.7–25 eV range have shown that the non-radiative energy transfer between host matrix and dopant molecules occurs via singlet states of SiO2 oxygen-deficient centers.