<p>The safe transportation of large volumes of hydrogen gas is crucial for a hydrogen-based economy, with low-carbon steel pipelines at high pressures being the most economic option. However, the risk of hydrogen embrittlement poses a significant challenge, requiring conservative operating limits that reduce their viability. To facilitate steel testing, a comparative analysis of high-pressure gaseous charging and the readily available electrochemical charging is necessary. This study compares hydrogen uptake characteristics after gaseous charging to three different electrochemical charging conditions using thermal desorption analysis based on total and diffusible hydrogen measurements. The results revealed distinct differences in hydrogen uptake across the electrochemical conditions, which were heavily influenced by the applied current density and steel microstructure. These differences in desorption behavior were attributed to differences in atomic hydrogen evolution on the steel surface. Both gaseous and electrochemical charging exhibited similar hydrogen trapping behavior and the potential for equivalence. However, certain electrochemical conditions resulted in higher rates of atomic hydrogen evolution, which promoted the accumulation of hydrogen at the steel’s subsurface layers, exceeding the levels observed with gaseous charging.</p>