During the last few years, graphene's unusual friction and wear properties have been demonstrated at nano to micro scales but its industrial tribological potential has not been fully realized. The macroscopic wear resistance of one atom thick graphene coating is reported by subjecting it to pin‐on‐disc type wear testing against most commonly used steel against steel tribo‐pair. It is shown that when tested in hydrogen, a single layer of graphene on steel can last for 6400 sliding cycles, while few‐layer graphene (3–4 layers) lasts for 47 000 cycles. Furthermore, these graphene layers are shown to completely cease wear despite the severe sliding conditions including high contact pressures (≈0.5 GPa) observed typically in macroscale wear tests. The computational simulations show that the extraordinary wear performance originates from hydrogen passivation of the dangling bonds in a ruptured graphene, leading to significant stability and longer lifetime of the graphene protection layer. Also, the electronic properties of these graphene sheets are theoretically evaluated and the improved wear resistance is demonstrated to preserve the electronic properties of graphene and to have significant potential for flexible electronics. The findings demonstrate that tuning the atomistic scale chemical interactions holds the promise of realizing extraordinary tribological properties of monolayer graphene coatings. The mechanism of extraordinary wear resistance of just one atom thick graphene layer on steel is revealed. A single layer of graphene is able to reduce steel wear by 3–4 orders of magnitude. The wear‐life of graphene significantly increases when tested in hydrogen environment. Hydrogen plays a crucial role in preventing graphene from wear‐induced damage by passivating carbon dangling bonds.