In this study, we examined the distribution behavior of sediment organic matter (SOM) between dissolved and particulate phases and the potential influencing factors by comparing the spectroscopic features of pore water organic matter (PWOM) and alkaline-extractable organic matter (AEOM) of river sediments. The characteristics of SOM were described by several selected spectral indicators and fluorescence excitation emission matrix (EEM)-parallel factor analysis (PARAFAC). The spectral indicators showed that larger sized SOM molecules with a higher aromatic content were more enriched in sediment particles than in pore water. The relative ratios of humification index between dissolved and particulate phases revealed that the SOM constituents with a higher degree of structural condensation were preferentially distributed onto sediment particles. EEM-PARAFAC demonstrated different distribution behaviors of protein-like (tyrosine-like and tryptophan-like) and humic-like substances in sediments. The relative abundance of tyrosine-like component was much higher in PWOM than in AEOM, whereas the other three components tended to be more abundant in AEOM. The predominant presence of tyrosine-like component suggests its potential operation as a discriminant indicator between PWOM and AEOM. Spearman correlations and non-metric multidimensional scaling further revealed that distribution of protein-like components onto sediment particles might be associated with reductive environments, aluminum minerals, and anthropogenic activities of upstream watersheds. This study demonstrated a successful application of using EEM-PARAFAC to examine the distribution behavior of different SOM constitutes between dissolved and solid phases.