High specific surface area makes carbon nanofibres suitable for catalyst support. Here we report on optimization of carbon nanofibre (CNF) growth on molybdenum carbide nanowires (MoCNW) by direct carburization of nanowire bundles. Typical CNFs obtained by this method are several hundreds of nanometres long at a diameter of 10–20 nm. We show that nanofibre growth does not depend on the initial morphology of the nanowires: nanofibres grow on individual bundles of MoCNW, on dense networks of nanowires deposited on silicon substrate, and on free-standing nanowire foils. We find that carbon nanofibres remain firmly attached to the nanowires even if they are modified into and further into nanowires. The method thus enables production of a novel hybrid material composed of nanowires densely covered with carbon nanofibres. We have additionally shown that the obtained CNFs can easily be self-decorated with platinum nanoparticles with diameters of several nanometres directly from water solution at room temperature without reducing agents. Such efficient synthesis and decoration process yield hybrid platinum/CNF/molybdenum-based NW materials, which are a promising material for a wide range of possible future applications, including sensitive sensorics and improved catalysis.