The trend in development of portable and wearable sensors in healthcare-related applications promotes an expanding demand for flexible, stretchable and electrically conductive fabrics. A novel structured conductive nickel-deposited poly(ethylene terephthalate) (PET) membrane intertwined with microbial pili-like poly(vinyl alcohol-co-ethylene) (PVA-co-PE) nanofibers has been prepared. FTIR and XRD analysis indicated that the deposited metallic nickel was semi-crystalline with a FCC structure. SEM observations showed that nickel was compactly deposited on the surfaces of the nanofibers and PET substrate in the Ni@nanofibers/PET membranes. The coated nanofibers acted as conductive bridges among the randomly entangled PET fibers, leading to a significant increase in the conductivity of Ni@PVA-co-PE nanofibers/PET membranes. Abrasion tests suggested that Ni@PVA-co-PE nanofibers/PET membranes have superior stability in electrical conductivity compared to that of the native Ni@PET membrane. The membrane with high conductivity and good stability was employed as an electrode to construct a capacitive alcohol sensor. The sensor demonstrated good sensitivity and high efficiency.