Potassium–lithium aluminoborate glasses with the composition (30-x)K2O-xLi2O-5Al2O3-63B2O3-1Ce2O3-1Dy2O3 glasses (labeled as KLABx:Ce,Dy, where x = 5, 10, 15, 20, and 25) were successfully synthesized via the melt–quenching method. The glass–ceramic phase was obtained by annealing the precursor glass at the crystallization temperature. The phase structure of the materials was confirmed by X-ray diffraction. The mixedalkali effect was clearly observed through FTIR, absorption, and emission spectra, as well as the thermoluminescence process. The emission intensity and color coordinates of the KLABx:Ce,Dy glass could be tuned by varying the Li2O/K2O concentration ratio. The changes in the physical properties and network structure of the glasses, as a function of the proportion of each alkali metal, were also discussed in detail. Thermoluminescence (TL) properties and dosimetric properties such as sensitivity, dose response, reusability, and fading, etc., have also been studied towards the application of the material for the manufacture of TLDs. The ceramicization of glass by annealing at the crystallization temperature has significantly improved the dosimetric performance of the material. The research results show the prospect of applying this material to the manufacture of environmental radiation dosimeters and radiation field determination.