Three-dimensional self-standing polypyrrole/Prussian blue (PPy/PB) aerogel monoliths have been fabricated through self-assembly of PPy/PB hydrogel precursors and subsequent freeze-drying. The hydrogel precursors are synthesized using methyl orange as the self-degraded template in the presence of ferricyanide as the oxidant. The morphology, crystalline structure and chemical composition of the resulting PPy/PB aerogels have been investigated by scanning electron microscopy (SEM), X-ray powder diffraction (XRD), Fourier-transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). Moreover, the as-prepared PPy/PB aerogels exhibit well-defined response in the electrocatalytic reduction of hydrogen peroxide (H2O2) owing to the combination of the electrochemical properties of PB and the conductivity of PPy in the aerogels. These aerogels with the multifunctional quality are expected to have wide applications in sensor and other related fields.