A series of chiral Schiff-base boron difluoride complexes was synthesized and their photophysical properties were examined. These complexes showed multi-colour (blue, yellow and red) photoluminescence in solution and in the solid state with good emission quantum yield (Φ) depending on the π-systems of the ligands. The chiral complexes exhibited circularly polarized luminescence (CPL) with an absolute luminescence dissymmetry factor (glum) of up to the 1.3 × 10-3 in solution and 1.9 × 10-2 in the drop-cast film state. Density functional theory (DFT) and time-dependent (TD) DFT calculations were conducted to further understand the photophysical properties.