[en] Highlights: • Developing a method to embed molybdenum trioxide nanoparticles into nanofibers for selective deposition over small areas; • Investigating effects of different process parameters on the fibre morphologies including MoO₃/PEO concentration; • Developing a simple modified set-up using two rings to control the location and spot size down to few millimetres. 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.