A new anthraquinone appended oxacalix[4]arene (DAQOC) has been synthesized and characterized by different ¹H NMR, IR, ESI-MS and ¹³C NMR spectroscopic techniques. This compound was explored for its sensing abilities towards various anions. DAQOC showed selective anion sensing behaviour towards F^- ions which was supported by absorption as well as emission studies. Among other anions, only in the presence of F^- ions, a quenching in the fluorescence emission of over 79% was observed due to changesin the intermolecular charge transfer (ICT) process. DAQOC exhibited high selectivity and good sensitivity toward F- ions in the presence of competing ions and the detection limit was found to be 1.23 lM. ^-H NMR titration displays that the peak corresponding to –NH protons (at 12.91 ppm) disappears upon interaction with F-, suggesting that the sensing mechanism follows the deprotonation route. The geometrical features of F- bound oxacalixarene species were modelled by the Density Functional Theory (DFT) and NCIPlot calculations. The findings suggested that the appended substituents including nitro groups and anthraquinone can make the calix[4]arene ring electron deficient and thereby more susceptible for F^- ions. Moreover, this present chemosensor has been applied for recognition of F^- ions from waste water samples which is of directpractical relevance.