The properties of the oxide films formed on solution-annealed and cold-worked 316L stainless steel (SS) specimens with and without charged hydrogen in deaerated pressurized water reactor primary water at 300 °C were investigated. The outer oxide layers of all specimens were composed of magnetite (Fe3O4) and NiFe2O4. Charged hydrogen resulted in larger outer iron-bearing oxide particles forming due to hydrogen-enhanced outward diffusion of iron cations. Prior cold-work accelerates the oxidation was observed. Charged hydrogen led to local cracks in the oxide film and enhanced the penetration oxidation beneath the metal/oxide interface. The Cr-rich inner oxide layer grown on the prior cold-worked specimen with charged hydrogen was thicker than that on the cold-work specimen or the hydrogen-charged specimen, revealing the combined effects of charged hydrogen and prior cold-work on the acceleration of the oxidation process. The working mechanism of the solid-state hydrogen effect on the oxide film was discussed.