The chemical compatibility of silver electrodes and low-firing ceramics has been considered, in terms of the existence of a tie line between silver (and/or Ag2O) and the binary oxide compound in the corresponding ternary phase diagram. The probability of the existence of the tie line is related to the conditions in the subordinated silver-based isothermal binary systems. Greater probabilities have been calculated for the systems with fewer silver-based binary compounds. Based on the concepts that have been developed, several silver-based isothermal binary systems have been investigated to identify the oxides suitable for the development of low-temperature cofired ceramics. The developed concept has been tested by investigating the phase relations in the Bi2O3–Nb2O5 and Bi2O3–V2O5 ternary systems with silver. X-ray and microstructural investigations of bismuth niobates and bismuth vanadates reveal that, as a result of the inertness of Bi2O3 and the reactivity of Nb2O5 and V2O5 toward silver, compounds that are rich in niobium or vanadium react with silver to form ternary Nb/V-Bi-Ag oxide compounds, whereas for compounds that are rich in bismuth, tie lines to silver and Ag2O do exist.