In this letter, we compare the structures of plasma-enhanced chemical vapor deposition of Ni-catalyzed and Pd-catalyzed carbon nanofibers (CNFs) synthesized for on-chip interconnect applications with scanning transmission electron microscopy (STEM). The Ni-catalyzed CNF has a conventional fiberlike structure and many graphitic layers that are almost parallel to the substrate at the CNF base. In contrast, the Pd-catalyzed CNF has a multiwall nanotubelike structure on the sidewall spanning the entire CNF. The microstructure observed in the Pd-catalyzed fibers at the CNF-metal interface has the potential to lower contact resistance significantly, as our electrical measurements using current-sensing atomic force microscopy indicate. A structural model is presented based on STEM image analysis.