CuFeO2 delafossite type nanowires with a diameter of 180 nm were successfully synthesized by electrospinning using an equimolar mixture of molecular copper and iron precursors and polyacrylnitrile as polymer template followed by calcination. This mixture was electrospun under ambient conditions. The copper and iron precursor complexes diaqua- bis[2-(methoxyimino)-propanato] M( II) (M=Cu,Fe) were fully characterized by spectroscopic and electrochemistry methods (NMR, IR, cyclovoltammetry) as well as by single crystal structure and by thermogravimetric analysis (TGA). The pre-ceramic electrospun composite fiber mats were subsequently heat treated in a two step procedure to yield the final CuFeO2 delafossite type nanowires agglomerated as microsized ceramic mats. Intermediate oxide phases as well as the finally obtained CuFeO2 fibrous mats composed of delafossite type nanowires were characterized analytically by temperature dependent powder X-ray crystallography (PXRD). Their topological morphology was studied by scanning electron microscopy (SEM). The obtained CuFeO2 fibrous mats were studied with respect to their O-2 gas sensing behaviour and variable p and n-type semiconducting behaviour depending on temperature was observed.