In order to investigate the structural change of dissolved organic matter after electron transfer, dissolved organic matter (DOM) were extracted fromlandfilled wastes at different depthsduring initial landfill stage, and shewanella Shewanella MR-1 and citrate iron (FeCit) were used as electron donor and electronacceptor, respectively. Furtherover, fluorescence excitation-emission matrix (EEM) spectra combined with parallel factor (PARAFAC) analysis was used to analyze the structure change of DOM. The results indicated that four fluorescent components, i.e., two humic-like components (C2 and C4) and two protein-like components (C1 and C3), were identified by the PARAFAC analysis, and protein-like components was the major component. The nitrogen-containing heterocyclic structure was desassembled when protein-like components got electrons, and theirhydrophobicity and fluorescence intensities were increased during the process. Fluorescence intensities of humic-like components were increased as well when they obtained electrons, though their increased range became decrease during the landfill processs. The carbonyl group on humic-like components were turn into alcohol group when it obatained electrons. Fluorescence quenching phenomenon was observeredwhen DOM loss electrons. Protein-like components wereable to offerelectrons, and theirstructure changed after they loss electrons. Humic-like substances can offer electrons as well, and their fluorescence intensities decreased as well when they loss electrons. However, the decreased range was related to the content of carboxyl and phenolic groups on humic-like subtaneces. Humic-like components could bereoxided, However, protein-like components could not be reduced after they was oxided. The electron shuttle capacityof DOM were ascribed to humic-like components, which were persistentlyincreasedduring the landfill process.