The results concerning the synthesis, structure and thermal properties of V2O5-MoO3-Ag2O samples in the vanadium rich region of ternary system are presented in the form of quasi-binary phase diagrams in which at constant V2O5/MoO3 molar ratios, equal 9:1, 7:3 and 1:1, the content of Ag2O was variable. A new ternary phase isostructural with NaVMoO6 has been detected in the investigated system.