The present contribution reports, for the first time, the mechanical and electro-rheological properties of electrospun poly(vinyl alcohol) (PVA) nanofibre mats with or without the incorporation of carbon black (CB) nanoparticles. The effects of sonication and the addition of CB on morphological appearance, average diameter of the as-spun fibre mats, and that of the individual fibres, were thoroughly investigated. Incorporation of CB (1-10% based on the weight of PVA) in 10% w/v PVA solution did not affect the morphology and average diameter of the obtained fibres (similar to 160 nm), but it affected both the mechanical and the electro-rheological properties of the as-spun PVA/CB fibre mats, in which the mats became more rigid with the addition and increasing amount of CB.