Hydrogen-terminated diamond is known for its p-type surface conductivity, which arises from a near-surface hole accumulation layer induced by adsorbed acceptor species. Here, we demonstrate that these surface acceptors also form optically active donor-acceptor pairs (DAP) with substitutional nitrogen donors in diamond. The insertion of a nominally undoped CVD interlayer between a nitrogen-rich HPHT substrate and a hydrogen-terminated surface enables the precise tuning of the donor-acceptor separation with nanometer precision. Radiative DAP recombination appears as bright, spectrally narrow lines whose intensity, energy, and decay dynamics depend systematically on interlayer thickness. Individual lines show single-photon statistics, while ensembles exhibit strong polarization anisotropy reflecting the planar donor-acceptor geometry. These findings reveal an optical counterpart of hydrogen-induced surface transfer doping in diamond and establish a surface-defined, nanometer-tunable platform for engineering DAP-based quantum emitters.