Superionic conduction in the amorphous AgI-Ag2O-CrO3 electrolyte system has been studied. The glass-former-to-modifier ratio and the concentration of AgI were varied continuously to establish the glass-forming domain of the system. X-ray diffraction and differential scanning calorimetry were used as sensitive probes. Transport studies and infrared absorption spectroscopy were used to characterise xAgI-(100-x)(Ag2O-CrO3) glasses to help clarify the conduction process and the possible structural units of these electrolytes. © 1993.