Nanoparticles composed of molybdenum oxide, MoO_x, were successfully prepared by room-temperature ionic liquid (RTIL)/metal sputtering followed by heat treatment. Hydroxyl groups in RTIL molecules retarded the coalescence between MoO_x NPs during heat treatment at 473 K in air, while the oxidation state of Mo species in MoO_x nanoparticles (NPs) could be modified by changing the heat treatment time. An LSPR peak was observed at 840 nm in the near-IR region for MoO_x NPs of 55 nm or larger in size that were annealed in a hydroxyl-functionalized RTIL. Photoexcitation of the LSPR peak of MoO_x NPs induced electron transfer from NPs to ITO electrodes.