Selenium-rich chalcogenides have gained popularity as materials for selector devices due to their unique Ovonic Threshold Switching behavior. Bulk Se86-xTe14Snx glassy alloys (0 ≤ x ≤ 6) were prepared through the traditional melt quenching method. The samples with Sn atomic percentage (x) = 3 to 6 are found to exhibit a rapid and reversible transition between a highly resistive and conductive state affected by an electric field. A remarkable decrement in threshold voltage (Vth) from 453 V to 62 V has been observed with increase in the Tin content. Differential scanning calorimetry (DSC) analysis was carried out to understand the variation of Glass transition temperature (Tg), Crystallization temperature (Tc), and other important glass stability parameters and their compositional dependence. Se82Te14Sn4 sample was found to be thermally most stable with Herby’s parameter value (HR) of 0.3860 and a maximum number of switching cycles at room temperature. X-Ray diffraction patterns of annealed samples were compared with pristine glass to study the multi-phasic Se–Te–Sn alloy. Further, the threshold voltage (Vth) and the number of threshold switching cycles are found to decrease with an increase in temperature till crystallization on-set temperature (Toc). The temperature-dependent conductivity studies showed an abrupt increase in the conductivity of the samples as the temperature crossed the crystallization onset temperature.