An effective and facile in situ electroless deposition approach for the fabrication of multi-walled carbon nanotube-supported Prussian blue nanoparticle (MWNTs/PB NP) composite nanomaterials is demonstrated in this article. The coverage of PB NPs on MWNTs is tunable by varying the experimental parameters, such as the initial molar concentration of FeCl3 + K3[Fe(CN)6], the relative concentration of FeCl3 + K3[Fe(CN)6] to MWNTs, and the temperature and duration of the heat treatment. This method involves a simple mixing process followed by a mild heating process and does not need the exhaustive surface oxidation process of MWNTs. TEM, FTIR, UV, and XRD are all used to characterize the MWNTs/PB composite materials. In addition, the electrochemical behavior of PB and catalysis of the reduction of H2O2, are investigated. The novel method is expected to be applicable for preparation of other coordination polymer/MWNTs composites and finds use in applications for electronic nanodevices.