A simple approach is demonstrated for effectively growing large-area vertically aligned carbon hexagonal nanoprism arrays on molybdenum substrates by the catalyst-assisted pulsed laser deposition techniques. The carbon hexagonal nanoprisms have uniform shape and length, almost aligned vertically on the substrate, and the average diameters are about 30 nm. The internal angles of the nanoprisms present 60 degrees. The vertically aligned nanorods have also been obtained for a comparison in the presence of catalyst Fe. The sample with vertically aligned carbon hexagonal nanoprism arrays exhibits better field emission behaviors than that with aligned carbon nanorod arrays. (C) 2009 Elsevier B.V. All rights reserved.