Novel synthetic approaches for the effective construction of MoOx – organic hybrid structures and MoOx nanosheets (NSs) have been developed. A solvothermal (ST) treatment of molybdenum trioxide utilizing dodecylamine (DDA) as an intercalating agent leads to the formation of MoOx – DDA hybrid structures. Layer spacing as a function of organic molecule lengths can be controlled by changing the surfactants located between the nanosheets. Maintaining the integrity of the parent crystal, hexagonal-shaped molybdenum oxide NSs up to four micrometers in lateral size separate following sonication of the hybrid structures. Formation of MoOx–oleylamine (OAm) highly oriented nanosheets with plasmonic behavior were also achieved using a rapid ST treatment of molybdenum trioxide in the presence of OAm surfactant. The effects of time and temperature on the formation, morphology, and crystal structure of well-ordered nanosheets were explored. These synthesized hybrid nanostructures and NSs are expected to show great potential for a variety of applications including rechargeable batteries, catalysis, and nanodevices.