The polymer matrix effect on the selectivity, response rate and reproducibility for coextraction type anion-selective optode membranes were investigated with DOA-plasticized PVC, PVC/hydroxylated PVC, PU/hydroxylated PVC and DOS-plasticized CTA matrices. Optode membranes were prepared with TDMACl and ETH2412 dissolved in one of the four solvent polymeric matrices. The PU/hydroxylated PVC and PVC-based membranes have almost the same selectivity coefficients, while the CTA-based membrane is more selective toward lipophilic anions. The membrane with PU/hydroxylated PVC adhered strongly to a glass surface, and showed highly reproducible and relatively rapid response. Very poor adhesion of PVC/hydroxylated PVC and CTA-based membranes limited the usability of those membranes as sensor components. Based on these results, and considering the biocompatibility for clinical samples, the optode made with PU/hydroxylated PVC was applied to determine the thiocyanate ion in human saliva. The results obtained with this simple device were comparable to those with rather complicated ISE methods.