4-mercaptoaniline functionalised platinum particles of 2 nm diameter were synthesised and over-grafted with 2-thiophenecarbonyl chloride. The derivative particles were dispersed in DMSO and gave long term stable suspensions. The Langmuir-Blodgett technique was then used to build up stable Langmuir-Blodgett films and the electrochemical behaviour of these ultra-thin films towards oxygen reduction was investigated in an acidic medium. It revealed direct activity without any previous activation treatments despite of the presence of the organic shell at the particle surface. Furthermore, XPS experiments revealed that the organic crown was not significantly destroyed on prolonged cycling. The results open a way to study original and versatile platinum-based nanocomposites.