Co-doped ZnO nano-agglomerates were synthesized by a facile solution process. Several characterization techniques revealed the successful doping of the ZnO by Co ions. FESEM results showed the agglomeration of the Co-doped ZnO nanoparticles to form large-sized nano-agglomerates. The diameters of the spherical nanoparticles and the agglomerates were not found to be uniform. The diameters of the nano-agglomerates ranged from ~25 nm–120 nm. XRD spectrum confirmed the Wurtzite hexagonal phase of ZnO in Co-doped ZnO nanoagglomerates. The average particle size for Co-doped ZnO nano-agglomerates was 20.68 nm. The sensing parameters were examined by using Co-doped ZnO nano-agglomerates modified gold electrode through cyclic voltammetric and amperometric analysis. The sensitivity of 70.73 μAmM−1cm−2 and very low-detection limit of 0.2 μM was observed for H2O2. The corresponding linear dynamic concentration range was 0.2–1633 μM. The excellent sensing activities of the Co-doped ZnO nano-agglomerates for H2O2 were attributed to the improved intrinsic electric properties and increased inner defects density, particularly near the interface region.