In this work, carbon nanotubes and minor amount of Fe/C core-shell structure nanoparticles were simultaneously synthesized by catalytic pyrolysis of ferrocene. Through high-resolution TEM observation and ED characterization, the results showed that the well-crystallized iron nanoparticles could catalyze the formation of carbon nanotubes, while the amorphous iron nanoparticles could not catalyze the formation of carbon nanotubes but form the Fe/C core-shell nanoparticles. (C) 2011 Elsevier Ltd. All rights reserved.