Dissolved organic matter(DOM) of municipal solid waste(MSW) consists of minerals, water, ash and humic substances, and is known to enhance plant growth. In this study, inoculating microbes (Z J, MS) were used in municipal solid wastes composting, and composting implemented a industrialized technology. During composting, dissolved organic matter was extracted from the compost and purified. The spectral characteristics of dissolved organic matter was determined by fluorescence emission, excitation, and synchronous spectroscopy. Fluorescence emission, excitation, and synchronous spectra characterized by different relative fluorescent intensities and peaks over time. Fluorescence spectra were similar to that of fulvic acid in sewage sludge, indicating the presence of dissolved organic matter with aromatic structures and a high degree of molecular polymerization. Compared with the controls with no microbial inoculation,the microbe-inoculated treatments exhibited the increase of aromatic polycondensation, in the following order: MS + ZJ > ZJ > MS >CK.