Herein, we report a vibration‐induced emission molecule, 9,14‐diphenyl‐dihydrodibenzo[a,c]phenazines (DPAC) compound‐catalyzed C−H difluoroalkylation of (hetero)arenes under visible light condition. This method demonstrates the promising potential of vibration‐induced emission molecules in photocatalysis and facilitates a metal‐free synthetic approach for difluoroalkyl (hetero)arenes with broad substrate scope and functional group tolerence.