One of the key challenges to practical electrochemical N2 reduction reaction (NRR) is to lower the overpotential and suppression of the side reaction known as the hydrogen evolution reaction (HER) during the NRR. The experimental NRR activity has been consistently shown to reach a maximum at early stage before reaching the mass-transfer limit and decreases with large overpotentials for many heterogeneous catalysts. Though the volcano-type current-potential relationship shown for NRR is unusual with limited reaction rates at higher overpotentials, the mechanistic origin has not been clearly explained, making the design principles for practical NRR still lacking. Herein, we investigate the potential-dependent reaction activity of NRR and HER using the constant electrode potential method and microkinetic modeling. It manifests the dominating proton adsorption over dinitrogen at small overpotentials leading to the inadequate reaction selectivity towards NRR at many metal catalyst surfaces. A clear potential-dependent competition between the N2 adsorption and *H formation is characterized by the degree of charge transfer in the adsorption process. It is also demonstrated that the larger charge transfer in *H formation is a general phenomenon applied to all heterogeneous catalyst surfaces considered here, that poses a fundamental challenge to realize practical electrochemical NRR. We suggest several strategies to overcome the latter challenges based on the present understandings.