Herein, we have developed a novel synthetic route for the synthesis of chromeno[4,3-d]pyrido[1,2-a]pyrimidin-6-one derivatives 8a-q using an acid ionic liquid [CMMIM][BF4 -] 4 via one-pot, three-component synthesis in aqueous ethanol at room temperature. A series of 17 derivatives have been successfully prepared with up to 93% yield. All the synthesized derivatives were well characterized using 1H-NMR, 13C-NMR, and FT-IR spectral techniques. Additionally, the photophysical properties of 12 selected derivatives including molar extinction coefficient (ε), Stokes shift (Δυ̅), and quantum yield (Φ) varying from 0.52095 × 104 to 0.93248 × 104, 4216 to 4668 cm-1, and 0.0088 to 0.0459, respectively, have been determined. Furthermore, the experimental data are supported by density functional theory (DFT) and time-dependent DFT calculations. Theoretical investigations showed a trend similar to experimental results.