The study investigates the influence of atmospheric plasma spray (APS) parameters on the structure and chemistry of coatings produced from a bismuth-containing 45S5 bioactive glass (Bi-BG). A melt-derived glass modified with the addition of 6.3 wt.% Bi2O3 was used as the feedstock powder, selected for its previously demonstrated radiopacity, cytocompatibility, angiogenic and antibacterial activity. The coatings were deposited on titanium alloy substrates using combinations of parameters that varied plasma current, Ar/H2 gas mixture ratio, and stand-off distance (SOD). Phase composition, morphology, and short‑range network structure were examined using XRD, SEM, DSC, and Raman spectroscopy. Short SODs combined with high plasma net power reduce the coating deposition efficiency and increase porosity, while longer distances favored amorphous phase retention and improved intersplat bonding. Raman spectroscopy revealed significant changes in phosphate and silicate network units, particularly in symmetric P–O–P and asymmetric Si–O–Si groups. Optimal coatings were obtained at moderate plasma net power (24.7 – 29.9 kW), and a long SOD of 120 mm, where the amorphous network was largely preserved, porosity was reduced, and mechanical integrity at the coating-substrate interface was enhanced. These findings offer practical insights into optimizing APS parameters for the fabrication of structurally stable, bioactive, and radiopaque glass coatings suitable for implantable biomedical devices.