We use a unique combination of electrochemical techniques to elucidate the dependency of hydrogen evolution reaction (HER) and absorption on pH and overpotential for iron and nickel. Impedance spectroscopy shows the dominance of the Volmer–Heyrovsky reaction pathway, challenging the common consideration of Volmer–Tafel dominance. Polarization slopes agree with the Volmer or Heyrovsky rate-determining step, with limitations at high overpotential. The evolution of steady-state permeation current density with overpotential is rationalized through newly-developed theory. Surface activity and absorption trends are captured. Combined with modelling, this work provides a path for quantifying hydrogen uptake and establishing an equivalent fugacity for aqueous electrolytes.