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Thermally sprayed aluminium (TSA) coatings provide protection to offshore steel structures without the use of external cathodic protection (CP) systems. These coatings provide sacrificial protection in the same way as a galvanic anode, and thus hydrogen embrittlement (HE) becomes a major concern with the use of high strength steels. The effect of TSA on the HE of steel seems to remain largely unknown. Further, the location of hydrogen in TSA-coated steel has not been explored. To address the above knowledge gap, API 5L X80 and AISI 4137 steel coupons, with and without TSA, were prepared and the amount of hydrogen present in these steels when cathodically polarised to −1.1 V (Ag/AgCl) for 30 days in synthetic seawater was determined. One set of TSA-coated specimens was left at open circuit potential (OCP). The study indicates that the amount of hydrogen present in TSA-coated steel is ~100 times more than the amount found in uncoated steel, and that the hydrogen seems to be largely localised in the TSA layer.