Synthesis of angular furoquinolinone derivatives with a new skeleton structure was accomplished via Williamson reaction of hydroxyquinolinones with α‐haloketones, such as 3‐chloro‐2‐butanone and phenacyl bromide, followed by treatment with polyphosphoric acid (PPA). The synthesized angular furoquinolinones were photooxygenated in chloroform or dimethyl formamide and in the presence of tetraphenylporphyrin (TPP) as a singlet oxygen sensitizer (1O2). The photooxygenation reactions furnished the photocleaved product through the [2 + 2] cycloaddition reaction. All photoproducts were isolated and fully characterized by spectral analyses.