Fluorescent materials are continuously contributing to important advances in the field of bioimaging. Among these materials, dioxaborine-based fluorescent materials (DBFM) are arousing growing interest. Due to their rigid structures conferred by a cyclic boron complex, DBFM possess appealing photophysical properties including high extinction coefficients and quantum yields as well as emission in the near infrared, enhanced photostability and high two-photon absorption. We herein discuss the recent advances of DBFM that found use in bioimaging applications. This review covers the development of fluorescent molecular probes for biomolecules (DNA, proteins), small molecules (cysteine, H2O2, oxygen), ions and the environment (polarity, viscosity) as well as polymers and nanomaterials used in bioimaging. This review aims at providing a comprehensive and critical insight on DBFM by highlighting the assets of these promising materials in bioimaging but also by pointing out their limitations that would require further developments.