Electrospinning is utilized to fabricate catalytic nanofiber scaffold for biocrude upgrading in hydrodeoxygenation (HDO) following computational studies suggesting the need for nano-catalysts for efficient HDO conversion and selectivity. Here, Pt-TiO2 nanofibers are fabricated through electrospinning, followed by wet impregnation with a heteropoly acid (HPA), tungstosilicic acid. Intensive heat treatments were incorporated during and after processes to obtain a HPA doped Pt-TiO2 nano-catalyst. Catalytic HDO was performed in a batch reactor with phenol as the raw biocrude dissolved in hexadecane. The HPA doped Pt-TiO2 catalyst demonstrated promising HDO performance of 37.2% conversion and a 78.9% selectivity to oxygen free benzene and the remainder 21.1% as diphenyl ester as a result of esterification by acidic components of the catalyst. Additionally, BET surface area characterization show a low surface area 16.9 m2 g−1 significantly lower than existing commercial catalysts and a mesoporous nature suitable for selectivity. The presence of HPA on the anatase nanofiber compensated for low platinum nanoparticles crystallinity on the nanofibers. This work might create needed alternatives for preparing HDO catalysts for efficient aromatics production.