Four ligands (M-1-M-4) have been synthesized and characterized by IR, H-1 NMR, spectroscopic investigations indicate good affinity of these ligands for fluoride anion. Different polyvinyl chloride (PVC) based membranes of ligands have been synthesized using different cationic excluders; CTAB, TDMAC, HTAB, ToMACl and plasticizers; DBBP, DBP, o-NPOE, CN, DOP, TEHB and investigated as F- selective sensors. The best performance is observed by the sensor with a membrane of composition (%, w/w) M-1:PVC:o-NPOE:CTAB 3.5:30.0:63.0:3.5. The sensor generates linear potential response over a wide concentration range of 2.5 x 10(-7) to 1.0 x 10(-2) M with Nernstian slope (59.8 mV decade(-1) of activity) over a pH range of 2.5-6.5 with a fast response time of similar to 11 s. It shows good selectivity for fluoride anion (F-) in preference to many anions. The sensor exhibits a shelf life of two and half months and could be successfully used for the comparative determination of fluoride in different Indian tea samples. The proposed method is faster, cheaper, and more accurate in comparison to already used methods. (C) 2012 Elsevier Ltd. All rights reserved.