A successful electrospun polyoxymethylene (POM) nanofiber using a hexafluoroisopropanol (HFIP)-based solvent is reported. The nanofibers obtained show a significant nanoporous surface as a consequence of the spinning conditions, i.e. spinning voltage and relative humidity, as well as the polymer/solvent properties. The oxyethylene unit in the polyoxymethylene copolymer decreases the nanofiber surface roughness and porosity, leading to a significant change in the specific surface area. A slight change in the molecular weight of the POM after electrospinning confirms that the nanofiber with nanoporous POM barely degrades or decomposes during the spinning. The electrospun POM nanofiber gives an inevitable nanoporous structure with high specific surface area (as much as 2-3 times higher) compared to those of the nonporous electrospun nylon-6 and porous electrsopun PAN reported in the past.