High field electrical switching studies on x Ag2O - (50-x) P2O5 -50V(2)O(5) glasses have been carried out as a function of sample thickness, composition and temperature. The I-V characteristic show that switching in these glasses is memory type. The switch voltages are found to decrease with increase of temperature, on the other hand, the voltages increase with the thickness of the sample. The experimental findings clearly reveal that switching in these glasses is a thermally assisted bulk effect. The results obtained are explained on the basis of formation of crystalline conducting channels. Another notable observation is that the glass with 15 mol% Ag2O concentration only exhibits the switching property at room temperature. This aspect is examined in view of various structural groups present in these glasses with the help of spectroscopic studies; IR and MAS-NMR measurements have been carried out. IR studies of these glasses show characteristic absorption peaks corresponding phosphate and vanadium vibrations in the network. P-31 MAS-NMR chemical shift show presence of [POO3/2](0)and [POO2/2O](-)groups.