Although heterocyclic hemiboronic acids are represented in several recently approved drugs, many questions remain unanswered regarding the physical properties and reactivity of these boranol (BOH)-containing compounds in aqueous media. Over the past 60 years, studies on the acidic and aromatic character of 10-hydroxy-10,9-boroxarophenanthrene and its boraza analog have been conflicting. In contradiction with the Lewis acidic behavior of arylboronic acids in aqueous conditions, it has been proposed that the central boroheterocyclic ring of these borophenanthroids confers sufficient aromatic character to compel the boranol unit to behave as a Brønsted acid and favor the boron oxy conjugate base, thereby avoiding the disruption of cyclic resonance that would otherwise occur with a tetravalent boronate anion. These questions are addressed with a combination of physical and spectroscopic characterizations, X-ray crystallographic analysis, and computational studies. Although both oxa and aza derivatives are conclusively shown to behave as Lewis acids in aqueous solutions, according to pKa measurements and MO and NICS calculations, only the boraza derivatives possess an appreciable aromatic character within the boroheterocyclic ring. For the first time, the possibility of dynamic chemical exchange via a reversible hydrolysis of the endocyclic B-heteroatom bond was examined using VT and EXSY NMR with suitable probe compounds. Whereas the boraza analog is static at neutral pH, its oxa analog undergoes a rapid hydrolytic ring opening-closing equilibrium with the transient boronic acid. Altogether, this study will guide the methodical application of these heterocycles as reaction catalysts, in bioconjugation, and as new-drug chemotypes and bioisosteres of pharmaceutically important classes of heterocycles.