Semiconductor dual-functional photocatalysis composed of selective organic oxidation and reduction has attracted increasing a ttention owing to the green and environmental advantages. Herein, the Nd@g-C ₃N ₄ dual-functional photocatalysis enabled fluoroalkylative heteroarylation of alkenes with R _fSO ₂Cl under visible-light and ultrasound conditions was firstly reported. The photogenerated electron-driven reductive production of fluoroalkyl radical paired with photogenerated hole-driven oxidative production of chloride radical resulted in the full utilization of photogenerated carrier for bond formation. The use of sono-photocatalysis enhances both energy efficiency and the rate of chemical reactions. A wide range of N-heteroarenes, alkenes and R _fSO ₂Cl, were well compatible for this reaction to access valuable fluoroalkylated N-heteroarenes with diverse structural features. We anticipate that this report will provide a sustainable synthetic protocol for fluoroalkylated N-heteroarenes but also develop the photoinduced chloride radical-mediated reaction and the dual-functional photocatalysis.