Platinum-coated carbon nanotubes (Pt/CNTs) with desired particle size and preferred surface crystallographic orientations have a variety of applications in diverse fields. Pt/CNTs having uniform dispersion of Pt nanoparticles are synthesized via electrodeposition route using CNT coated carbon fiber as the working electrode and H(2)PtCl(6 center dot)6H(2)O as Pt precursor. Particle size and crystallographic orientation of Pt nanoparticles are controlled by using polyvinylpyrrolidone (PVP) as the protecting agent during electrodeposition in H2SO4 or HCl containing coating baths. Cyclic voltammetric study and X-ray diffraction analysis suggest Pt(100) surface enrichment of Pt nanoparticles in presence of PVP, which increases with increasing PVP concentration. Although the Pt deposition rate decreases significantly in presence of Cl- ions, the enrichment effect is observed both in the H2SO4 as well as the HCl containing baths. The Pt/CNT synthesized in presence of PVP exhibit higher oxygen reduction reaction activity (acidic media) and methanol oxidation activity compared to that synthesized without PVP. The process may be utilized to synthesize Pt based electrocatalysts with controlled particle size and preferred surface orientation. (C) 2015 Elsevier Ltd. All rights reserved.