A dc plasma enhanced chemical vapor deposition process is used to obtain vertically aligned carbon nanofibers (CNFs) from palladium catalysts using an ammonia–acetylene process gas mixture. Transmission electron microscopy is used to elucidate the microstructure of the as-grown fibers revealing different growth anomalies such as a new secondary growth phenomenon which we term hybrid tip growth. Also included in our analysis are conventional tip growth derived structures. In a few instances, the conventional tip growth derived structures possess elongated catalyst particles that impart small cone angles to the carbon nanofiber microstructure. Detailed microchemical analysis reveals that hybrid tip grown CNFs using thick Pd films are partially filled with Pd. Analysis of these growth phenomenon and implications for potential use as on-chip interconnects are discussed.