The quaternary superion conducting (SIC) 66.67%AgI-22.22%Ag2O-11.11% [(x)CrO3 + (1 - x)V2O5] (x = 0.1-0.9 in steps of 0.1) (SCV) glassy system was prepared in various former (CrO3 + V2O5) compositions by melt quenching method. All the prepared compounds were characterized by XRD and IR techniques to find out the nature and the structure of the SCV compounds. The electrical conductivity was measured as function of frequency as well as temperature for the former compositions of the SCV compounds. The 66.67%AgI-22.22%Ag2O-11.11% [0.3CrO(3) + 0.7V(2)O(5)] composition of the SCV compound is found to have highest conductivity (sigma = 1.01 x 10(-2) S/cm) at room temperature and it is well comparable to the bulk conductivity [sigma= 1.01(+/-0.009) X 10(-2) S/cm] obtained from the impedance measurements. The variation of conductivity with the former composition of the SCV system was explained using the random site model.