Abstract: We present a first experimental investigation on the Tl site in Tl-doped borosilicate glass by Tl/Na ion-exchange process. The local order around Tl was investigated by the EXAFS spectroscopy on a set of different samples, obtained by varying the composition of the molten salt bath (TlNO3/NaNO3 molar ratio from 0.001 to 0.4) and the bath temperature (between 350°C and 380°C). We show that after a 1h exchange, Tl is surrounded by O atoms in the first shell and that the Tl–O distance is sensibly shorter than both the Tl–O distance found in Tl oxides and the typical Na–O distance in a glass. When the exchange process is extended to 1 week, the measured Tl–O distance increases towards the values found in crystalline Tl oxides, suggesting a stress release during longer exchange duration. [Copyright &y& Elsevier]