Graphene quantum dots (GQDs) were synthesized via the oxygen-driven unzipping of graphene under ultra-high frequency ultrasonication, and then attached to the SiC nanoparticles by the hydrothermal method to form the SiC/GQDs nanocomposites. The SiC/GQDs exhibited superior photoactivity over the decomposition of perfluorooctane sulfonate (C8F17SO3H, PFOS), which was even harder to decompose than perfluorooctanoic acid (PFOA). This work presented the first instance of employing photoexcited semiconductor nanomaterials to realize the improvement from the activation of the -F2C-COOH bond in PFOA to the activation of -F2C-SO3H in PFOS. The decomposition rate constants (k) of 2-CF3-PFOS, 6-CF3-PFOS and linear-PFOS with SiC/GQDs were 0.127 h(-1), 0.115 h(-1), 0.098 h(-1), and the corresponding half-lives were 5.5 h, 6.0 h, 7.1 h, respectively. The ratio of k (the branched isomers: the linear isomers) significantly reduced from the 967 times via vacuum ultraviolet (VUV) photolysis to the same order of magnitude in this work. The X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) were conducted to investigate the electronic properties of SiC/GQDs, revealing the center most directional electron transfer process during the reaction. The photogenerated electron originated from the pi-pi* transition of the C=C bond and the n-pi* transition of the C=O bond under UV excitation, transferred to SiC nanoparticles due to the heterojunction structure of SiC/GQDs, and then further transferred to the accumulated PFOS on the surface of SiC/GQDs for the electron-withdrawing property of sulfonate group, leading to the critical activation of sulfonate group. The decomposition mechanisms of PFOS involved the ionic headgroup cleavage, hydrolysis, hydrodefluorination, and the C-C bond scission. (C) 2017 Elsevier B.V. All rights reserved.