Well-crystallized and hexagonal wurtzite ZnO was synthesized with nanocellulose using a facile hydrothermal method. Many highly active (001) facets were retained in the obtained ZnO nanocrystals, presumably due to interaction between the polar facet of ZnO and the nanocellulose. Given its effective surface area, the synthesized ZnO exhibited good photocatalytic activity of degrading methylene blue. Its degradation efficiency reached 94.4% within 30 min (UV irradiation power of 6 W), which was 34% higher than that of Degussa TiO2 P25. The ZnO photocatalyst also exhibited excellent reusability, confirmed by no obvious abatement after its being re-used for 8 cycles. These ZnO nanomaterials were synthesized using renewable nanocellulose derived from cotton. This environmentally friendly and cost-effective approach is anticipated to be applied in the future synthesis of small-sized ZnO photocatalysts.