This paper presents the initial results of the synthesis of β-Ga2O3 luminescent ceramics via plasma gas-thermal spraying synthesis, where low-temperature plasma of an argon and nitrogen mixture was employed. A direct current electric arc generator of high-enthalpy plasma jet with a self-aligning arc length and an expanding channel of an output electrode served as a plasma source. The feedstock material consisted of a polydisperse powder of monocrystalline β-Ga2O3 with particle sizes ranging from 5 to 50 μm. The study presents the results of both theoretical and experimental studies on the heating rate and average temperature of gallium oxide particles in a plasma jet. The results of computational modelling of the synthesis process of β-Ga2O3 via plasma gas-thermal spraying are shown. The obtained ceramic samples were characterized using scanning electron microscopy and X-ray diffraction analysis. Our results indicate that the synthesis process yielded ceramics with a layered texture. The stoichiometric composition of ceramics exhibited a shift towards gallium-rich content. X-ray diffraction data demonstrated a reduction in the lattice parameters and unit cell volume of β-Ga2O3 ceramic structure. Radioluminescence spectra of β-Ga2O3 ceramics revealed an intensive emission band with a maximum at ~360 nm and non-exponential decay. The synthesized β-Ga2O3 ceramics possess potential applications in scintillation detectors.