The hot and dense plasma formed in modified dense plasma focus (DPF) device has been used worldwide for the nanofabrication of several materials. In this paper, we summarize the fabrication of III–V semiconductor nanostructures using the high fluence material ions produced by hot, dense and extremely non-equilibrium plasma generated in a modified DPF device. In addition, we present the recent results on the fabrication of porous nano-gallium arsenide (GaAs). The details of morphological, structural and optical properties of the fabricated nano-GaAs are provided. The effect of rapid thermal annealing on the above properties of porous nano-GaAs is studied. The study reveals that it is possible to tailor the size of pores with annealing temperature. The optical properties of these porous nano-GaAs also confirm the possibility to tailor the pore sizes upon annealing. Possible applications of the fabricated and subsequently annealed porous nano-GaAs in transmission-type photo-cathodes and visible optoelectronic devices are discussed. These results suggest that the modified DPF is an effective tool for nanofabrication of continuous and porous III–V semiconductor nanomaterials. Further opportunities for using the modified DPF device for the fabrication of novel nanostructures are discussed as well.