This work elucidates the influence of exposed facets of anatase-TiO crystals on the efficiency and selectivity of reduction of functionalised nitrobenzene derivatives. Titanium dioxide crystals in the form of bipyramids, sheets, and belts offering different exposed facets {001}/{101}, {001}, and {100}, respectively, were synthesised. Electrochemical analysis revealed a slight positive shift in the reduction potential of belt TiO. The highest photocurrents were observed for sheets, whereas in the presence of methanol, the photocurrent doubling effect was observed for belts and bipyramids, with the most efficient methanol oxidation in the case of belts. The highest reaction rate constant for the reduction of 3-nitrophenol and 1-iodo-4-nitrobenzene was also noticed for belts. The observed differences in the resulting photocatalytic activity of nitroaromatics reduction were attributed to different efficiencies of methanol oxidation taking place at the tested photocatalysts.