A key element in the rational design of hybrid organic-inorganic nanostructures is control of surfactant packing and adsorption onto the inorganic phase in crystal growth and assembly. In layered single crystal nanofibers and bilayered two-dimensional (2D) nanosheets of vanadium oxide, we show how the chemisorption of preferred densities of surfactant molecules can direct the formation of ordered, curved layers. The atom-scale features of the structures are described using molecular dynamics simulations that quantify surfactant packing effects and confirm the preference for a density of 5 dodecanethiol molecules per 8 vanadium attachment sites in the synthesized structures. This assembly maintains a remarkably well ordered interlayer spacing, even when curved. The assemblies of interdigitated organic bilayers on V 2O 5 are shown to be sufficiently flexible to tolerate curvature while maintaining a constant interlayer distance without rupture, delamination, or cleavage. The accommodation of curvature and invariant structural integrity points to a beneficial role for oxide-directed organic film packing effects in layered architectures such as stacked nanofibers and hybrid 2D nanosheet systems. © 2012 American Chemical Society.