In this study, for highly stable HAT-DSPEC process, metal based sensitizer was replaced by organic dye(5-[4-(diphenylamino)phenyl]thiophene-2-cyanoacrylic acid, L1) which has high stability and molar absorption coefficient. For regenerating dye molecules and oxidating lignin model compounds(LMCs), bicyclic nitroxyl derivates, such as 2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO), and 9-azabicyclo[3,3,1]nonan-3-one-9-oxyl (Keto-ABNO) was used. In HAT-ODSPEC (organic dye-sesitized photo-electrochemical cell), Keto-ABNO exhibits higher photo-electrocatalytic activity than TEMPO for the oxidation and decomposition of LMC. The superior activity of L1 sensitizer with Keto-ABNO mediator is especially noteworthy of Caryl-Cα bond cleavage and with keto-ABNO exhibits 100% conversion yield of for 24hrs at room temperature while 86% with TEMPO. This HAT-ODSPEC process provides a unique foundation to perform selective C−C bond cleavage for real lignin conversion technologies.