This study reports an environment-friendly synthetic strategy to process nickel oxide nanocrystals. A mesoporous nickel oxide nanostructure was synthesized using an environmentally benign biomimetic method. We used a natural rambutan peel waste resource as a raw material to ligate nickel ions to form nickel-ellagate complexes. The direct decomposition of the obtained complexes at 700 °C, 900 °C and 1100 °C in a static air atmosphere resulted in mesoporous nickel oxide nanostructures. The formation of columnar mesoporous NiO with a concentric stacked doughnuts architecture was purely dependent on the suitable direct decomposition temperature at 1100 °C when the synthesis was carried out. The prepared NiO nanocrystals were coated on cotton fabric and their antibacterial activity was also analyzed. The NiO nanoparticle-treated cotton fabric exhibited good antibacterial and wash durability performance.