The effects of charging and outgassing on the friction and wear of Ni-P amorphous and nanocrystalline coatings were studied under ambient humidity and temperature. The results indicate that hydrogen charging can greatly decrease the volume loss during friction and increase the wear durability. However, the wear durability can be restored after outgassing. There are many cracks on the brittle nanocrystalline before charging, and no crack appears after charging, but there are only a few cracks on the outgassed sample. This indicates that hydrogen charging can inhibit the crack formation during friction for the brittle Ni-P nanocrystalline. For the charged sample, after the surface layer was removed by polishing, the wear track and the friction coefficient are consistent with those ofan uncharged sample. The friction coefficient of the charged amorphous coating is very small within the first 140 s and then increases suddenly to the value corresponding to the uncharged sample. The absorbed surface layer lubricates the surface, reduces the friction coefficient, and improves the wear durability.