Trapping centres in undoped Ga4Se3S single crystals grown by Bridgman method were characterized for the first time by thermoluminescence (TL) measurements carried out in the low-temperature range of 15-300 K. After illuminating the sample with blue light (similar to 470 nm) at 15 K, TL glow curve exhibited one peak around 74 K when measured with a heating rate of 0.4 K/s. The results of the various analysis methods were in good agreement about the presence of one trapping centre with an activation energy of 27 meV. Analysis of curve fitting method indicated that mixed order of kinetics dominates the trapping process. Heating rate dependence and distribution of the traps associated with the observed TL peak were also studied. The shift of peak maximum temperature from 74 to 113 K with increasing rate from 0.4 to 1.2 K/s was revealed. Distribution of traps was investigated using an experimental technique based on cleaning the centres giving emission at lower temperatures. Activation energies of the levels were observed to be increasing from 27 to 40 meV by rising the stopping temperature from 15 to 36 K.