This article summarizes the results obtained studying the interaction between polonium and stainless steel 316L in different atmospheres by the thermochromatography method. This issue is particularly important in terms of licensing of the MYRRHA prototype ADS reactor, where highly radiotoxic α-emitting polonium isotopes are produced in lead-bismuth eutectic used as both spallation target material and coolant, while stainless steel 316L is going to be the main structural material. The polonium adsorption enthalpy on stainless steel 316L in inert atmosphere was measured as −147±6 kJ mol−1. The findings obtained using reducing atmospheres show that the affinity of polonium for stainless steel 316L increases with the metallic character of the stainless steel surface. The presence of moisture in inert and reducing atmosphere does not significantly influence the polonium adsorption. Oxidizing atmospheres induce the formation of polonium dioxide which has a stronger interaction with the stainless steel 316L, with an adsorption enthalpy of −225±6 kJ mol−1. A prolonged exposure of the stainless steel to strong oxidants, such as pure oxygen, reduces the metallic character of the stainless steel surface and, consequently, its affinity to the polonium oxide. Furthermore, it was found that in all experiments at least 5 ppm of the total polonium present in the starting material were not retained on the stainless steel 316L surface at all.