Two diaza-crown ether compounds were synthesized and evaluated as Ag+-selective carriers in polyvinylchloride (PVC) membrane electrodes of solid-state type. The all-solid-state PVC membrane electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 exhibited a super-Nernstian response (7510mV per decade) over the concentration range of 1101 to 7106M of Ag+ ion and a detection limit of 3106M, at a wide range of pH (pH 47). The response time of the electrode was fast (less than 10s), and it can be used for three months without any significant deviation in potential. The proposed all-solid-state PVC membrane electrodes revealed high selectivity toward Ag+ ion with respect to alkali, alkaline earth, heavy and transition metal ions. A flow-through cell of all-solid-state PVC membrane Ag+-selective electrode based on N,N-Dibenzyl-dibenzo-diaza-18-crown-6 has also been prepared and applied for flow-injection analysis of Ag+ ion in solution.