This study examined the utilization of spent coffee grounds with different aqueous extraction methods for the bioelectricity generation from coastal benthic sediment through a sediment microbial fuel cell (SMFC) system. Different methods for the aqueous extraction of SCGs were evaluated, including rinsing and drying of the SCG (SMFC-CRD), immersion, rinsing and drying (SMFC-CRID), drying alone (SMFC-CD), and untreated SCG (SMFC-C). The caffeine concentration in the SCG was significantly reduced using pretreatments, with SMFC-CRID achieving the lowest concentration of 0.021 ± 0.001 mg/g. SMFC-CRD contributed to the generation of the highest current density of 213.7 mA/m during closed-circuit operation and exhibited the highest power density of 96.9 mW/m in the polarization test, due to the suitable caffeine content of 0.275 ± 0.001 mg/g in the SCG. This study could provide a cost-effective method for reusing SCGs (i.e., 128 g) while generating bioelectricity as an alternative energy source. These results suggest that pretreatment with SCGs is essential for achieving optimal power density and reducing the caffeine concentration in the SMFC system.