In the present work, scanning tunneling microscopy (STM) was employed to study the surface modification of ultrahigh modulus carbon fibers at the atomic level by oxygen plasma. As detected by STM, the distinctive feature of the fresh, untreated surface was the general presence of atomic-scale arrangements in different degrees of order (from atomic-sized spots without a clearly ordered disposition to triangular patterns identical to those typical of perfect graphite). Following fiber exposure to the plasma, the STM images showed evidence of the abstraction of carbon atoms from random locations on the fiber surface, giving rise to the development of defects (i.e., structural disorder), which in turn were the places where oxygen could be introduced during and after the plasma etching. It was observed that the most effective treatments in terms of extent of surface structural modification (disordering) and uniform introduction of oxygen were those carried out for just a few (similar to 3) minutes. Considerably shorter exposures failed to provide a homogeneous modification and many locations on the fiber surface remained unaltered, retaining their original atomic-scale order, whereas longer treatments did not bring about further structural changes to the surface and only led to fiber consumption. These results are consistent with previous X-ray photoelectron spectroscopy measurements on these fibers and provide an atomic-level understanding of the saturation effect observed in the surface oxygen concentration of this and other types of carbon fibers with plasma oxidation. Such understanding may also prove helpful for the accurate control and optimization of fiber-matrix interaction in composite materials. (C) 2003 Elsevier Science (USA). All rights reserved.