MgB 4 O 7 doped with rare earths and alkaline elements has been reported as a good TLD because of its high sensitivity, effective atomic number close to that of biological tissue and low fading. In this work, thermoluminescent matrices were synthesized of MgB 4 O 7 :Dy and MgB 4 O 7 :Dy, Na to evaluate their thermoluminescent response (TL) when exposed to γ-rays and neutrons. The amount of Dy was studied in a concentration range of 0.01–1.5 mol% of total doping, while for Na the concentration of 0.5 mol% was established to determine the TL response as a function of doping. The synthesis of the powders was carried out by the method of wet reaction assisted by heat treatment and the samples were characterized by techniques of scanning electron microscopy and X-ray diffraction to determine the size of grain and crystallographic phase. For the dosimetric study, thermoluminescent phosphors were irradiated with a source of ¹³⁷ Cs at an estimated dose 6.8 ± 0.4 mGy to evaluate their response to γ-rays exposure, while for neutrons a source of ²⁴¹ AmBe was used (estimated dose of 3.1 ± 0.1 mGy). The thermoluminescent responses are similar for all materials exposed to γ-rays as for neutrons, the differences are shown to 280 °C, where a peak of high temperature is observed in materials exposed to neutrons.