This work highlights the enabling aspects of borylated building blocks such as borane nitrilium rapidly access to structurally diverse boron heterocycles with useful photophysical properties. The borindolizine scaffold is constructed in a single synthetic step from readily accessible substituted 2-methylpyridines. This deep-seated disconnection allows for significant changes in the scaffold as well as in the fluorescence emission wavelengths resulting in two new classes of emitters -violet-blue (carboxyborindolizines) and cyan-green (aryl borindolizines) with high Stokes shifts. Subsequently, the experimental emission values were used to validate a computational model for predicting photophysical spectra. Through this model, a new class of small molecule red-emitters was developed through a synthetically-validated scaffold modification approach. Altogether, borindolizines represent a boroncontaining heterocyclic platform for the synthesis of tunable fluorophores and should serve as an inspiration for unique approaches to targeted chromophore design.