Abstract Syntheses of 2,3‐dimethyl‐4 H ‐furo[3,2‐ c ]coumarin and 3‐phenyl‐4 H ‐furo[3,2‐ c ]coumarin as angular furocoumarins were carried out through Williamson reaction of 4‐hydroxycoumarin with α ‐haloketones followed by cyclization. Photooxygenation of the synthesized furocoumarin derivatives was performed and the photoproducts were isolated and characterized. The affinity of 2,3‐dimethyl‐4 H ‐furo[3,2‐ c ]coumarin towards DNA and the antibacterial activity were evaluated and compared with 8‐methoxypsoralen (8‐MOP).