N-type semiconducting molybdenum trioxide (MoO3) nanoparticles embedded in polyethylene oxide (PEO) polymer ultra-fine fibres were deposited directly onto silicon substrates using an electrospinning technique. The effects of different MoO3/PEO concentrations as well as electrospinning parameters on the fibre morphologies were examined. Experimental results show that embedding nanoparticles and electrospinning onto small areas can be achieved without use of solvents or transfer of the deposited nanostructures. This approach offers a cost effective fabrication method to produce a diverse range of multifunctional materials for many applications including electronics, mechanical enhancement, drug delivery and gas sensing.