Tris(3-aminopropyl)amine-based tripodal urea and thiourea receptors, tris([(4-cyanophenyl)amino]propyl)urea (L1) and tris([(4-cyanophenyl)amino]propyl)thiourea (L2), have been synthesized and their anion binding properties have been investigated for halides and oxoanions. As investigated by ¹H NMR titrations, each receptor binds an anion with a 1 : 1 stoichiometry via hydrogen-bonding interactions (NH⋯anion), showing the binding trend in the order of F⁻ > H₂PO₄⁻ > HCO₃⁻ > HSO₄⁻ > CH₃COO⁻ > SO₄²⁻ > Cl⁻ > Br⁻ > I in DMSO-d₆. The interactions of the receptors were further studied by 2D NOESY, showing the loss of NOESY contacts of two NH resonances for the complexes of F⁻, H₂PO₄⁻, HCO₃⁻, HSO₄⁻ or CH₃COO⁻ due to the strong NH⋯anion interactions. The observed higher binding affinity for HSO₄⁻ than SO₄²⁻ is attributed to the proton transfer from HSO₄⁻ to the central nitrogen of L1 or L2 which was also supported by the DFT calculations, leading to the secondary acid–base interactions. The thiourea receptor L2 has a general trend to show a higher affinity for an anion as compared to the urea receptor L1 for the corresponding anion in DMSO-d₆. In addition, the compound L2 has been exploited for its extraction properties for fluoride in water using a liquid–liquid extraction technique, and the results indicate that the receptor effectively extracts fluoride from water showing ca. 99% efficiency (based on L2).