Herein, we demonstrated a facile sonochemical preparation of manganese hexacyanoferrate (Mn-HCF) and examined its use as an intercalative-type electrode for Li-ion hybrid capacitors (LHCs). The X-ray diffraction, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopic analyses revealed the formation of Mn-HCF nanocubes. The electrochemical analyses revealed the presence of ion-intercalation pseudocapacitance in the Mn-HCF electrode with a specific capacity of 81.59 mAh g−1. In the view of practical applications, we designed a Mn-HCF∥graphene LHC which delivered a high specific capacitance (79.52 F g−1) and energy density (44.18 Wh kg−1), respectively. Overall, our results highlight the significance of Mn-HCF towards cost-effective energy storage devices.