The influence of synthesis methods on Materials Institute Lavoisier (MIL) nanostructures and their photoelectrochemical activities was examined under light-ON/OFF states. Additionally, the impacts of various electrolytes on the performance of the MIL electrodes and kinetic activities of the anodes were investigated. Compared with the samples prepared using the hydrothermal technique (MFH samples), the samples synthesized using the microwave-assisted technique (MFM samples) exhibited significantly higher electrochemical activities. In the ON state, the MFM sample in a 0.1 M NaOH electrolyte showed the lowest charge-movement resistance of 154.28 Ω, which was much lower than that of the MFH sample. The MFM sample generated a significantly higher photocurrent density in the NaOH electrolyte owing to its increased number of active sites, low resistance, and reduced Tafel slopes. Thus, MFM electrodes with robust and stable nanostructures are suitable for electrochemical applications.