An original approach has been proposed for designing a nanofibrous (NF) layer using UV-cured polyvinylpyrrolidone (PVP) as a matrix, incorporating mesoporous graphene carbon (MGC) nanopowder both inside and outside the fibers, creating a sandwich-like structure. This architecture is intended to selectively adsorb and detect acetic acid vapors, which are known to cause health issues in exposed workers. The nanocomposite MGC-PVP-NFs layer was fabricated through electrospinning deposition onto interdigitated microelectrodes (IDEs) and stabilized under UV–light irradiation. To enhance the adhesion of MGC onto the surface of the nanocomposite polymeric fibers, the layer was dipped in a suspension of polyethyleneimine (PEI) and MGC. The resulting structure demonstrated promising electrical and sensing properties, including rapid responses, high sensitivity, good linearity, reversibility, repeatability, and selectivity towards acetic acid vapors. Initial testing was conducted in a laboratory using a bench electrometer, followed by validation in a portable sensing device based on consumer electronic components (by ARDUINO®). This portable system was designed to provide a compact, cost-effective solution with high sensing capabilities. Under room temperature and ambient air conditions, both laboratory and portable tests exhibited favorable linear responses, with detection limits of 0.16 and 1 ppm, respectively.