Sodium‐metal batteries (SMBs) employing transition‐metal‐free cathodes are of great importance for energy storage applications that require low cost and high energy density. A strategy to enhance the energy density of transition‐metal‐free‐cathode SMBs by transforming the electrolyte from a dead mass to an energy‐storage contributor is reported. NaI is used for the partial substitution of NaClO4 in the electrolyte and thus provides the additional electrochemistry of I3−/I− redox couple to enhance battery performance. Graphene oxide (GO) encapsulated mesoporous (10 nm) carbon spheres (N‐MCS@GO) that are nitrogen‐doped (15.71 at%) are fabricated as the cathode for the I3−/I− redox enhanced SMBs. It is experimentally demonstrated that: the mesoporous structure increases the capacitive energy storage by providing a substantial interface that enhances the electrochemistry of I3−/I− redox couples; and encapsulation of the mesoporous carbon spheres with GO suppresses self‐discharge and increases Coulombic efficiencies from 70.4% to 91.9%. In full‐cell configuration, N‐MCS@GO working with the NaI‐activated electrolyte can deliver a capacity of 279.6 mAh g−1 with an energy density of 459.2 Wh kg−1 in 0.5–3 V at 200 mA g−1. I3−/I− redox in the full cell maintains its activity without obvious decay after 1000 cycles at 1 A g−1, highlighting the practical application of the I3−/I− redox enhanced SMBs.