A microwave-assisted oxidative cleavage process is developed to prepare graphene quantum dots (GQDs) from carbon black. The size evolution of the resulting carbonaceous products is studied. In one hour, GQDs of a size less than 10 nm and thickness less than 2 nm are obtained. These GQDs are further composited with mesoporous carbon aerogels (CA) by a filtration process to form GQD-decorated CA composites (GQD/CA). The GQD/CA composite is applied as a catalyst electrode for the reduction of I₃⁻ to I⁻, a critical electrolyte regeneration reaction in dye-sensitized solar cells (DSSCs). Also investigated are Pt electrodes, the expensive traditional counter electrode material for DSSCs, and plain CA electrodes for comparison. Based on data derived from cyclic voltammograms and Tafel plots, the GQD/CA composite exhibits catalytic efficiencies comparable to that of Pt electrodes and better than that of plain CA electrodes. The GQD/CA electrodes, however, surpass the Pt electrodes in terms of long-term stability. The cathodic current drops significantly after 500 cycles for the Pt and plain CA electrodes, whereas the cathodic current is slightly increased for the GQD/CA electrodes. The GQD/CA composite thus proves to be an inexpensive, efficient, and stable alternative to Pt as the counter electrode material for DSSCs.