The possibility of doping ZnO in its metastable rock salt structure with Li, Na, and K intended to act as acceptor dopants was investigated. For the first time, MgxZn1−xO alloys and pure ZnO with a rock salt structure doped with Li, Na, and K metals was obtained by high-pressure synthesis from pure oxides with the addition of carbonates or acetates of the corresponding metals as dopant sources. Successful stabilization of the metastable rock salt structure and phase purity were confirmed by X-ray diffraction. Transmission electron microscopy was used to study the particle size of nanocrystalline precursors, while the presence of Li, Na, and K metals in rock salt ZnO was detected by electron energy-loss spectroscopy and X-ray photoelectron spectroscopy in MgxZn1−xO alloys. Electron paramagnetic resonance measurements revealed the acceptor behavior of Li, Na, and K dopants based on the influence of the latter on native defects and natural impurities in ZnO-MgO alloys. In addition, diffuse reflectance spectroscopy was used to derive band gaps of quenched rock salt ZnO and its alloys with MgO.