The advent of benzoxaborole drugs sparked a renaissance surrounding heterocycles derived from boronic acids in organic and medicinal chemistry, where they demonstrate a wide range of biological properties. Our recent studies addressed unanswered questions regarding the physical properties, acidic nature (Lewis vs Brønsted), dynamic behavior, and reactivity of boranol (B–OH)-containing heterocycles in organic and aqueous media. These fundamental studies are essential for guiding a systematic application of select heterocycles as enantioselective reaction catalysts, in bioconjugation, and as new antimicrobial drug chemotypes and bioisosteres of pharmaceutically important classes of heterocycles. Ongoing investigations focus on new boroheterocyclic chemotypes and the exchangeability of B–OH bonds for direct catalytic activation of alcohols and diols.