This paper reports an investigation of the adsorption of hydrogen on iron during the hydrogen evolution reaction. The solution pH was 8.4. The investigation was carried out by means of FTIR spectroscopy. Fe‐H vibrations were identified at 2060 and 980 cm−1; and were compared with the values of estimates for stretching and bending vibrations in Fe‐H, respectively. The peak intensities varied with electrode potential. Assuming that the area under the peak at 2060 cm−1 is proportional to the hydrogen coverage, , on iron, a slope of was obtained for the plot of θ vs. η where η is the overpotential. Corresponding experiments with showed peaks which are relatable to those for hydrogen in an expected manner. An indirect estimate of the value suggested this to be about 0.3 at −0.9V. The results are consistent with a slow discharge‐atomic combination route for hydrogen evolution.