Carbonaceous-based nanomaterials (C-NMs) are the pillar of myriad sensing and catalytic electrochemical applications. In this field, the search for environmentally sustainable C-NMs from renewable sources became a duty in the development of nano-sensors. Herein, water-soluble carbon nanofibers (CF) were produced from eucalyptus scraps-based biochar (BH) through an ultrasound treatment, assisted by sodium cholate used as a stabilizing agent. The BH-CF was investigated as sensing material onto commercial screen-printed electrodes via drop-casting (BH-SPE) and as thin-film fully integrated into a lab-made flexible electrode. The thin film was produced via BH-CF vacuum filtration followed by the film transferring to a thermo-adhesive plastic substrate through thermal lamination. This approach gave rise to a conductive BH-CF film (BH-Film) easily embodied in a lab-made electrode produced with office-grade instrumentation (i.e. craft-cutter machine, thermal laminator) and materials (i.e. laminating pouches, stencil). The BH-CF amount was optimized and the resulting film morphologically characterized, then, the electrochemical performances were studied. The BH-CF electrochemical features were investigated towards a broad range of analytes containing phenol moieties, discrimination between orto‐ and mono-phenolic structures were achieved for all the studied compounds. As proof of applicability, the BH-CF-based sensors were challenged for simultaneous determination of mono-phenols and ortho-diphenols in olive oil extracts. LODs ≤ 0.5 μM and ≤ 3.8 μM were obtained for hydroxytyrosol (o-diphenol reference standard) and Tyrosol (m-phenols reference standard), respectively. Moreover, a high inter-sensors precision (RSD calibration-slopes ≤ 7 %, n = 3) and quantitative recoveries in sample analysis (recoveries 91-111%, RSD ≤ 6 %) were obtained. Here, a solvent-free strategy to obtain water-soluble BH-CF was proposed, and their usability to sensor fabrication and modification proved. This work demonstrated as cost-effective and sustainable renewable sources, rationally used, can lead to obtain useful nanomaterials.