A colorimetric anion sensor -meso-heptaethylcalix[4]pyrrole-meso-3- aminophenyl-p-nitrobenzaldoxime was synthesised and characterised by various spectroscopic techniques. Anion-binding studies were carried out using UV-vis, and 1H NMR titrations, revealing that the receptor exhibits selective recognition towards F- over other anions. The selectivity for F - among the halides is attributed mainly to the hydrogen bond interaction of the receptor with F-. Receptor showed colour change from colourless to yellow in the presence of tetrabutylammonium fluoride with 1:2 stoichiometry. Cyclic voltammetry studies, carried out in CH3CN, provided evidence of an anion-dependent electrochemical response with F- ion. This response was particularly dramatic in the case of receptor after the addition of ∼1 equiv. of FO ion. © 2013 Taylor and Francis.