Herein, template or surfactant free synthesis of porous platinum nanostructures has been reported from a liquid-liquid interfacial synthetic technique. Here the progress of the Pt4+ reduction has been governed by an aromaticity driven pathway of 2,4 dihydropyridine ester (DHPE) in dichloromethane (DCM). Thus morphologically two different Pt nanostructures at the liquid-liquid interface are evolved depending upon the imposed reaction conditions (UV irradiation or mild heat). Comparative methanol oxidation reaction (MOR) in basic condition illustrates that porous platinum nanochains (Pt NCs), synthesized under heat, show 14.63 and 1.43 times higher mass activity than platinum nanoparticles (Pt NPs) and platinum nanoflowers (Pt NFs), synthesized under UV irradiation. Furthermore Pt NCs exhibit remarkable catalytic stability for MOR and also superior catalytic efficiency for formic acid oxidation (FAOR) leaving aside CO poisoning. The assembly of Pt nanowires generates porous Pt NCs which provide the oppertunity for better utilization of expensive Pt in electrocatalysis in terms of its higher mass activity and stability compared to even commercial Pt/C catalyst. Thus our proposed synthetic procedure for naked and porous platinum nanostructure foretells its practical fuel cell application. (C) 2015 Elsevier Ltd. All rights reserved.