Dissolved organic matter (DOM) is a key component in reaction network of anaerobic digestion. In this study, fluorescent excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis and two-dimensional (2D) FTIR correlation spectroscopy were firstly used to explore chemical changes of soluble intermediates in high-solid biogas reactor. EEM-PARAFAC showed that fluorescent components (tyrosine-like, tryptophan-like and humic-like groups) in DOM over time increased gradually, implying that these groups were reluctant to biodegrade (acidogenesis). The resistance to biodegradation presented the following order: humic-like group>tyrosine-like group>tryptophan-like group. 2D FTIR correlation spectroscopy indicated that the DOM change sequence with time followed the order: protein-like groups>structural carbohydrates and carboxylic acids>polysaccharides-like groups. Fluorescence intensities from EEM-PARAFAC and main bands of FTIR spectra correlated significantly with other chemical parameters, e.g. biogas production and dissolved organic carbon content. These findings supply novel realization for degradation degree and order of individual DOMs during anaerobic digestion for dewatered sewage sludge.