MgB₄O₇ co-doped with Ce and Li has been recognized as a promising dosimetric material for spatially-resolved optically stimulated luminescence (OSL) measurements. Nevertheless, conflicting information exists in the literature regarding its dosimetric characteristics. These include discrepancies in fading, the proportion of shallow traps, the range of linear dose response, and a notable absence of direct sensitivity comparisons. These discrepancies are likely attributed to variations in the synthesis methods utilized to produce this material. As part of our research initiative aiming at elucidating the influence of synthesis on the luminescence properties, we are examining in this contribution a single parameter – specifically, the sample preparation temperature – and assessing its impact on the luminescence properties. For the first time, we identified a correlation between the width of the thermoluminescence (TL) glow curves, the TL, optically stimulated luminescence (OSL), and radioluminescence (RL) intensities, as well as the fading characteristics over time and annealing temperature. We show that annealing at higher temperature leads to narrowing of the main TL peak (c.a. 240 °C at 5 °C/s heating rate) compared with samples prepared at lower temperatures, which in turn leads to a decrease in the integrated TL intensity of that peak. Despite exhibiting lower intensity, samples prepared at temperatures above 800 °C show less than 10 % TL/OSL fading over 60 days. Our measurements suggest an involvement of clustered defects for the samples prepared at 600 °C, with a shift towards a scenario of delocalized transitions in samples prepared at higher temperatures.