Herein, a series of metallo-porphyrins, corroles and phthalocyanines were applied as the key precursors to confirm the influence of macrocyclic cores on the preparation of single- and dual-metal nitrogen-doped carbon (M-N-C) catalysts, and the control the M-N-C catalyst preparation towards accelerating electrocatalyzed hydrogen evolutions could be rationally modulated. Due to the synergetic effect, the dual-metal Co0.97Cu0.03TPP@rGO-900 M-N-C catalyst has the best performance on the electrochemically catalyzed hydrogen evolution with onset potentials as −166 mV and Tafel 117 mV·dec−1. More importantly, these M-N-C catalysts could also be used in a wide range of pH values, such as PBS and KOH medias.