Most ceramic-carbon nanotube (CNT) composite processing utilizes solid state sintering, hence the concept of wetting of CNTs by molten ceramic is absolutely new. In the present work on a plasma sprayed Al(2)O(3)-CNT nanocomposite, it is observed that molten Al(2)O(3) spreads uniformly on the CNT surface by forming a thin (∼20-25 nm) ceramic layer without any cracks. The wettability of the Al(2)O(3)-CNT system is associated with the surface tension and capillary forces as captured from the evolution of microstructure. The dynamic equilibrium between melting and solidification of Al(2)O(3) was deduced from the meniscus height, curvature, contact perimeter and projection area of solidified Al(2)O(3) on the CNT surface. This interfacial phenomenon illuminates the mechanisms of microstructure evolution from Al(2)O(3)-coated CNT bridge structures to CNT mesh formation. Consequent ab initio modeling depicted distorted iso-surface contours at the interface, suggesting partial bonding and good wettability of Al(2)O(3) on the CNT surface.