Hydrogen termination of diamond lowers its ionization energy, driving electron transfer from the valence band into an adsorbed water layer or to a strong molecular acceptor. This gives rise to p-type surface conductivity with holes confined to a subsurface layer of a few nanometers thickness. The transfer doping mechanism, the electronic behavior of the resulting hole accumulation layer, and the development of robust field-effect transistor (FET) devices using this platform are reviewed. An alternative method of modulating the hole carrier density has been developed based upon an electrolyte-gate architecture. The operation of the resulting “solution-gated” FET architecture in two contemporary applications will be described: the charge state control of nitrogen-vacancy centers in diamond and biosensing. Despite 25 years of work in this area, our knowledge of surface conductivity of diamond continues to develop.