A molybdenum dioxide/multiwalled carbon nanotubes (MoO2/MWCNT) hybrid composed of spherical flowerlike nanostructures of MoO2, interconnected by MWCNTs has been prepared by a one-step hydrothermal route. The growth of MoO2 nanoparticles into spherical floral shapes with a monoclinic crystalline structure is steered by the dioctyl sulfosuccinate surfactant. The one-dimensional electron transport pathways provided by MWCNTs, which are in direct contact with MoO2 nanostructures, impart an enhanced reversible lithium storage capacity (1143 mA h g-1 at a current density of 100 mA g-1 after 200 cycles), high rate capability (408 mA h g-1 at a high C-rate of 1000 mA g-1) and good cycling stability to the MoO2/MWCNT hybrid relative to neat MoO 2. Surface potential mapping of the electrodes by Kelvin probe force microscopy, revealed a lower localized work function for the MoO 2/MWCNT hybrid as compared to the neat oxide. This makes the MoO 2/MWCNT hybrid more easily oxidizable than neat MoO2. Such a distinctive topology achieved for the MoO2/MWCNT hybrid, wherein the MWCNTs prevent the agglomeration of MoO2 nanostructures and thus preserve good electrical connectivities, makes it different in terms of both morphology and performance from all previously reported MoO2-based anode materials to date. © 2013 American Chemical Society.