Visible light-mediated radical perfluoroalkylation reactions using heterogeneous graphitic carbon nitride

•Cyano-modified graphitic carbon nitride (g-NCNCNx) was developed for photocatalytic perfluoroalkylation reactions. .•Photocatalytic addition or coupling reaction can be achieved selectively and effectively with a broad substrate scope.•g-NCNCNx exhibits excellent photocatalytic activity for at least five catalytic cycles.•More photoelectrons of g-NCNCNx generated after light irradiation, improving the photocatalytic performance, comparing to pristine g-CNx.