We investigated the synthesis mechanism of Prussian blue (PB) crystals supported on single-walled carbon nanotubes (SWCNTs), by performing in situ quartz crystal microbalance (QCM) measurements to probe the change in the electrode mass during the reaction, and using photoirradiation at designated stages of the process. We found that in contrast to existing hypotheses, light irradiation played no role in the synthesis process of Prussian blue on SWCNTs. On the other hand, the number of electrons transferred per one mole of the obtained product, and the number of electrons transferrable from SWCNTs, calculated from the density of states (DOS) of the SWCNTs in the sample, both favor the hypothesis of the reaction being triggered by direct electron transfer from SWCNTs to Fe3+, which occurs because of the energy difference between the Fermi level of SWCNTs and redox potential of Fe3+ ions.