3-(2-(Ethynyl)phenyl)quinazolinones were designed and synthesized as a class of novel and efficient skeletons for phosphorylation/cyclization reactions. Under visible light irradiation, a series of phosphorylated quinolino[2,1-b]quinazolinones (35 examples, up to 87% yield) were first synthesized from 3-(2-(ethynyl)phenyl)quinazolinones and diarylphosphine oxides by using 4CzIPN as a photocatalyst under mild conditions. This reaction was also applicable under sunlight irradiation. Moreover, the reaction efficiency could be significantly improved under continuous-flow conditions.