Sediment microbial fuel cells (SMFCs) have received notable attention for improving water and sediment quality. However, their low performance must be improved. Adding steelmaking slag (SS) to littoral sediment reportedly improved the SMFC performance. However, the decomposition of the organic matter in sediment that fueled SS-used SMFC (SS-SMFC) has not been revealed. The present study examines changes in the state of organic matter present in paddy soil that fueled SS-SMFC. Furthermore, the effects of a series connection of a solar cell with SS-SMFC (SC-SMFC) on changes in the state of organic matter are also examined. Increasing the electrical current of the SMFC and the alkalinity of the paddy soil by SS better facilitated the decomposition of organic matter. Relative to SS-SMFC, SC-SMFC (generating the periodic current) better facilitated the decomposition of organic matter. However, SS-SMFC (generating continuous current) better improved the redox conditions of the paddy soil than SC-SMFC. The generated electrical current decomposed the organic matter which burns at high temperature, thereby increasing the amount of organic matter that burns at lower temperature. A similar trend was observed among SMFC, SS-SMFC, and SC-SMFC. It can be said that this effect is independent of the current characteristic (continuous or periodic).