Bismuth (Bi) exhibits a high theoretical capacity, excellent electrical conductivity properties, and remarkable interlayer spacing, making it an ideal electrode material for supercapacitors. However, during the charge and discharge processes, Bi is prone to volume expansion and pulverization, resulting in a decline in the capacitance. Deposition of a nonmetal on its surface is considered an effective way to modulate its morphology and electronic structure. Herein, we employed the chemical vapor deposition technique to fabricate Se-decorated Bi nanosheets on a nickel foam (NF) substrate. Various characterizations indicated that the deposition of Se on Bi nanosheets regulated their surface morphology and chemical state, while sustaining their pristine phase structure. Electrochemical tests demonstrated that Se-decorated Bi nanosheets exhibited a 51.1% improvement in capacity compared with pristine Bi nanosheets (1313 F/g compared to 869 F/g at a current density of 5 A/g). The energy density of the active material in an assembled asymmetric supercapacitor could reach 151.2 Wh/kg at a power density of 800 W/kg. These findings suggest that Se decoration is a promising strategy to enhance the capacity of the Bi nanosheets.