Novel rose thorns-like nanofibers, composed of polyarylene ether nitriles (PEN) "rose stems" and iron phthalocyanine (FePc) "thorns", are prepared by combining electrospinning and controlled temperature-induced self-assembly. After removing solvent and subsequent temperature treatment, the FePc sheath structure changes from bead structure to rose thorns-like structure. The unique nanoscale architecture can be finely controlled by the processing time and temperature. The length of "thorns" on the "rose stems" can change from several nanometers to decade micrometers. The driving force for the morphology changes comes from self-assembly of FePc, including the pi-pi supramolecular interaction between aromatic cores and the cooperative complexation of metal ions between peripheral crown ether moieties. This novel structure, rendering a 3-D feature, can offer potential in a number of applications, including nanoelectronics. (C) 2011 Elsevier Ltd. All rights reserved.