A DBU-mediated cascade strategy of propargylamines with dimethyl 3-oxoglutarate for constructing a functionalized benzo[c]chromen-6-one core has been achieved. This cascade process presumably involves a sequence of 1,4-conjugate addition, followed by lactonization, alkyne-allene isomerization, enol-keto tautomerization, 6π-electrocyclization, and aromatization. This protocol features mild reaction conditions, simple operation, rich structural diversity, and good functional group tolerance. A photophysical survey reveals that the benzo[c]chromen-6-one products exhibit fluorescence properties and show potential for exploring fluorescent material applications.