Carbon nanostructures were grown by using electroless Ni-P (Ni-Ni3P) alloys as catalysts. And the influence of the deposition structure on the as-grown nanostructures was examined. It reveals that traditional Ni-Ni3P alloy film on steel substrate could result in a preferred formation of carbon nanofibers, whereas, nanocrystalline Ni-Ni3P alloy catalysts could yield a formation of carbon nanotubes and especially those of nanotube junctions and double-helixed nanocoils. The successful use of these electroless alloys as catalysts here suggests wide catalysis applications of many binary or multinary alloys prepared through electroless plating and rapid quenching techniques. (C) 2003 Elsevier Science B.V. All rights reserved.