Titanium oxynitride carbon composite nanofibers (TiON/C-CNFs) were synthesised with electrospinning and subsequent heat treatment in ammonia gas. In situ four-probe electrical conductivity measurements of individual TiON/C-CNFs were performed. Additionally, the TiON/C-CNFs were thoroughly analysed with various techniques, such as X-ray and electron diffractions, electron microscopies and spectroscopies, thermogravimetric analysis and chemical analysis to determine the crystal structure, morphology, chemical composition, and N/O at. ratio. It was found that nanofibers were composed of 2–5 nm sized titanium oxynitride (TiON) nanoparticles embedded in an amorphous carbon matrix with a small degree of porosity. The average electrical conductivity of a single TiON/C-CNF was 1.2 kS/m and the bulk electrical conductivity of the TiON/C-CNF fabric was 0.053 kS/m. From the available data, the mesh density of the TiON/C-CNF fabric was estimated to have a characteristic length of 1.0 µm and electrical conductivity of a single TiON/C-CNF was estimated to be from 0.45 kS/m to 19 kS/m. The electrical conductivity of the measured TiON/C-CNFs is better than that of amorphous carbon nanofibers and has ohmic behaviour, which indicates that it can effectively serve as a new type of support material for electrocatalysts, batteries, sensors or supercapacitors.