Simulated by the synthesis of one dimensional hollow nanostructures with significant sensing, electrical, and optical properties, we have successfully synthesized 1D hollow nanostructures of h-MoO3/SnO2 with well-defined multi-side walls. These hollow nanostructured materials synthesized via a hydrothermal method with SnCl2.2H2O as the precursor and h-MoO3 as the template. SnO2 nanoparticles grew on the surface of h-MoO3 with preferential direction [001]. The morphological change was observed with variation of the growth conditions, such as HNO3, and h-MoO3 concentration. 1D hollow nanostructures of h-MoO3/SnO2 were studied and their growth mechanism was discussed. The result revealed that the existence of h-MoO3 caused to increase the sensor response to ethanol gas and downshift the sensor operating temperature at low temperatures.