The use of nanostructured carbon materials as electrodes for energy storage and conversion is an expanding area of research in recent years. Herein, platinum nanoparticles have been deposited onto both multi-walled and single-walled carbon nanotubes (CNTs) via a microwave assisted polyol reduction method. This interaction has been probed with electron paramagnetic resonance (EPR) and Raman spectroscopies to elucidate the charge/electron transfer interactions between the Pt nanoparticles and the CNTs. Observed shifts in the g factors of the CNTs are indicative of such an electronic interaction, strongly suggesting the covalent attachment of the nanoparticles to the carboxylic groups on the CNTs, formed during the microwave-assisted reduction process. The Pt decorated CNTs show a dramatic increase in electrochemical behaviour in terms of high reversible capacity and relatively stable cycle performance compared to unmodified CNTs increasing their applicability in energy storage devices. For instance, significant increases in the electrochemical double layer capacitance are observed for the CNT-NP composite electrode.