Owing to the small electronegativity of the sulfur atom, it is commonly supposed that at most one weak H-bond can be formed between a sulfur atom and an H-bond donor. In this paper, an unprecedented 2 : 1 binding species generated from two molecules of phenol and a molecule of thioether was observed and characterized by various nuclear magnetic resonance (NMR) techniques, Fourier transform-infrared (FT-IR) techniques and density functional theory (DFT) calculations, revealing the formation of sulfur-centred O-H⋯S⋯H-O bifurcated H-bonds. This work may provide a simple and efficient method for the quantitative analysis of weak H-bonds between small organic molecules.