TiO2 nanoparticles were prepared via an electrochemical method using pulse alternating current and applied in the photocatalytic oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-diformylfuran (DFF). Its physicochemical properties were characterized by SEM, HRTEM, XRD, and BET methods. The effect of scavenger and UVA light intensity was studied. The results revealed that electrochemically synthesized TiO2 nanoparticles exhibit higher DFF selectivity in the presence of methanol (up to 33%) compared with commercial samples.