AbstractIntriguing luminescent properties of boranil complexes have gained a prominence. Here, we report the synthesis and optical properties of star‐shaped boranil complexes. The strategy involves one‐step synthesis by a simple mixing triformylphloroglucinol with various aromatic amines in the presence of diisopropylethyl amine (DIPEA), and the complexing reagent of BF3⋅Et2O in chloroform at 80 °C for 24 hours. The complexes are obtained in good yields (60–85 %). These boranil complexes have strong fluorescence in both solution (λmax=466–605 nm) and solid (λmax=612–659 nm) states, with the fluorescence quantum yields varying from 1.5–57 % in chloroform. The emission color of the complexes has been tuned from blue to red by varying the aryl‐substituents in the complexes. Further understanding of the optical and electronic properties is obtained theoretically using DFT computations.