Chemical doping has been demonstrated to be an effective way to realize new functions of graphene as metal‐free catalyst in energy‐related electrochemical reactions. Although efficient catalysis for the oxygen reduction reaction (ORR) has been achieved with doped graphene, its performance in the hydrogen evolution reaction (HER) is rather poor. In this study we report that nitrogen and sulfur co‐doping leads to high catalytic activity of nanoporous graphene in HER at low operating potential, comparable to the best Pt‐free HER catalyst, 2D MoS2. The interplay between the chemical dopants and geometric lattice defects of the nanoporous graphene plays the fundamental role in the superior HER catalysis. Together they're strong: Nitrogen and sulfur co‐doped nanoporous graphene displays high catalytic activity in the hydrogen evolution reaction (HER) at low operating potential. The interplay between the chemical dopants and geometric lattice defects is crucial for the superior HER performance by minimizing the Gibbs free energy of H* absorption.