The effect of annealing on multi-walled carbon nanotube (MWCNT) arrays grown via catalytic Chemical Vapour Deposition (c-CVD) was studied. The treatment enabled to decrease number of defects/imperfections in the graphene walls of MWCNTs', which was reflected in Raman spectroscopy by reduction of the I-D/I-G ratio by 27%. Moreover, the vertical alignment from the as-synthesized nanotube arrays was found intact after annealing. Not only graphitization of the nanotube walls occurred under annealing, but the amount of metal iron-based catalyst residues (interfering with numerous physicochemical properties, and hence applications of MWCNTs) was reduced from 9.00 wt.% (for pristine MWCNTs) to 0.02 wt.% as detected by Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES). This value, established by a new analytical protocol, is the lowest recorded by now for purified c-CVD MWCNTs and, due to operating under atmospheric pressure, medium temperature regime (as for annealing processes), reasonable time-scale and metal residue non-specificity, it could lay the foundation for commercial purification of c-CVD derived MWCNTs. (C) 2014 Elsevier B.V. All rights reserved.