Reverse Monte Carlo (RMC) simulations were applied for modelling the atomic structure of the PbO-TeO2 glasses containing 10, 15 and 20-mol% PbO. The short-range order of the lead-tellurium-oxygen network, involving pair correlation functions of PbO, TeO and OO pairs, the average coordination numbers and the three-particle bond-angle distributions were determined by the RMC analysis. The average PbO coordination is in the range of 5.66 ± 0.19 to 6.02 ± 0.30, whereas TeO coordination (NTe-O) decreases steadily from 3.55 ± 0.04 to 3.36 ± 0.03 with increase in PbO concentration from 10 to 20 mol%. Raman studies also confirmed that NTe-O decreases on increasing PbO concentration, the latter acts as a modifier and disrupts the local tellurite speciation. The structural parameters are used in the Zwanziger model of stress-optic response to predict that PbO-TeO2 glasses should exhibit negative stress birefringence, a result which is in agreement with the experimental findings reported in the literature.