The synthesis of a simple ambidentate ligand 1-(3-methylsulfanyl-phenyl)-3-pyridin-2-yl-urea (L) capable of binding metal ions via a pyridyl nitrogen atom or thioether sulfur donor is reported. The pyridyl functionality is located adjacent to an anion bindingurea group allowing this region of the ligand to bind contact ion-pairs by simultaneous coordination and hydrogen bonding interactions. This intimate ion-pair binding coordination mode is demonstrated by the X-ray crystal structures of [Ag(L)]X (X = CH₃CO₂⁻, 1; NO₃⁻, 2). The non-coordinating PF₆⁻ anion is not bound as an ion-pair in [Ag(L)](PF₆) (3) and the urea NH groups exhibit short contacts to carbonyl oxygen and π-systems. The X-ray crystal structure of [Ag(L)₄]BF₄ (4) is also reported, showing the ligand to be exclusively S-bound. Anion binding by L and its silver(I) complex is also explored by solution ¹H NMR spectroscopic methods.