An analysis of crystal structures of a series of fluoro-substituted phenylboronic acids is presented. Interplay between the structure of a basic H-bonded dimeric R 2 2 (8) synthon and a higher-order supramolecular organization is highlighted. The elucidation of hydrogen bonds formed by the boronic B(OH) 2 moiety is supported by energy calculations based on a one-dimensional H-bond model as well as by Hirshfeld surface analysis. The results revealed that intramolecular O−H•••F hydrogen bonds are insignificant compared to O−H•••O ones in dimers in controlling the syn−anti conformation of the boronic group. Depending on the strength of H-bonds in the basic motif, forces constituting so-called large synthons change from O−H•••O hydrogen bonds to stacking interactions. This differentiation entails the twist of the boronic group with respect to the phenyl ring. The large synthons serve as main building blocks for three-dimensional structures either by their close packing or by the aid of weak secondary interaction such as C−H•••π, O−H•••F, or C−H•••F hydrogen bonds. The observed isomorphism and polymorphism are discussed in relation to the packing of one-dimensional large synthons.