This paper discusses the processes of the long-lived ¹³⁷Cs and ⁶⁰Co immobilization on titanium surfaces in simulated light water reactor primary circuit environments. This study is prompted by numerous problems in both the maintenance of equipment during reactor operation and the dismantling of the reactor after the completion of the operation, which is associated with contamination of working surfaces with long-lived radionuclides. The composition of the oxide films formed on the surface of commercial titanium alloy ΠT-3B has been studied with specimens prepared in autoclave test conditions and surface samples from the pipeline sections to which the primary coolant was applied. These films on the coolant pipeline surface consist of a titanium dioxide layer tightly adhered to the pipeline metal surface and weakly fixed deposits—crystallites comprised of titanium oxides and other corrosion products (oxides and hydrated oxides of iron, nickel, chromium etc.). The radionuclide composition of the samples was studied by gamma-spectrometry. It is shown that the mechanism of titanium-surface contamination with ¹³⁷Cs is by physisorption, contamination level increases upon the presence of dispersed particles. For ⁶⁰Co, both sorption and deposition onto surfaces are observed.