Thermoluminescence curves, kinetics, and Electron Paramagnetic Resonance (EPR) data were compared for Li₂B₄O₇:Mn and Li₂B₄O₇:Mn,Be radiation detectors. Analysis of the experimental data, both our own and published by other investigators, in connection with features of the crystal lattice structure allowed us to build models of traps and thermo­luminescence mechanisms. The thermoluminescence peaks used in dosimetry are connected with the release of holes trapped at bridging oxygen near Mn²⁺ (or Be²⁺), substituting for tetrahedrally coordinated B³⁺. The luminescence occurs at Mn²⁺ substituting for Li⁺. Two types of Mn²⁺ centres give different luminescence and EPR spectra. The effects of Mn²⁺ interaction with surrounding oxygen atoms are discussed both for the Mn²⁺ luminescence band and for the hyperfine structure of EPR. Kinetics measurements revealed an additional “hopping” barrier for a hole to get to a recombination centre after it has been released from a trap. A simple kinetics model is suggested to describe the experimental data. The studies of optical stimulation spectra and optically stimulated emptying of traps demonstrated the possibility of using Li₂B₄O₇:Mn and Li₂B₄O₇:Mn,Be radiation detectors with optically stimulated readout systems.