For nano-structured solids (those with one or more dimensions in the 1–100 nm range), attempts of surface modification can pose significant and new challenges. In traditional materials, the surface coating could be several hundreds nanometers in thickness, or even microns and millimeters. In a nano-structured material, such as particle or nanofibers, the coating thickness has to be substantially smaller than the bulk dimensions (100 nm or less), yet be durable and effective. In this paper, some aspects of effective nanometer scale coatings have been discussed. These films have been deposited by a non-line of sight (plasma) techniques; and therefore, they are capable of modifying nanofibers, near net shape cellular foams, and other high porosity materials. Two types of coatings will be focused upon: (a) those that make the surface inert and (b) those designed to enhance surface reactivity and bonding. The former has been achieved by forming 1–2 nm layer of — CF2 — (and/or CF3) groups on the surface, and the latter by creating a nanolayer of SiO2-type compound. Nucleation and growth studies of the plasma-generated film indicate that they start forming as 2–3 nm high islands that grow laterally, and eventually completely cover the surface with 2–3 nm film. Contact angle measurements indicate that these nano-coatings are fully functional even before they have achieved complete coverage of 2–3 nm. They should therefore be applicable to nano-structural solids. This is corroborated by application of these films on vapor grown nanofibers of carbon, and on graphitic foams. Coated and uncoated materials are infiltrated with epoxy matrix to form composites and their microstructure, as well as mechanical behaviors are compared. The results show that the nano-oxide coating can significantly enhance bond formation between carbon and organic phases, thereby enhancing wettability, dispersion, - nd composite behavior. The fluorocarbon coating, as expected, reduces bond formation, and therefore, effective as an inert layer to passivate nanomaterials.