The long-range ordered cuprous oxide nanostructured superlattice (L alpha-Cu(2)O) was synthesized using sodium dodecyl sulfonate (SDS; C(12)H(25)SO(3)Na) as supermolecular template in waterethanol media via a facile reflux method. CuCl(2), glucose and NaOH served as Cu source, reductant and precipitant, respectively. X-ray diffraction analysis showed that Cu(2)O is the sole inorganic phase in L alpha-Cu(2)O. Transmission electron microscopy further observed and proved this 2.7-nm period of regular nanostructured superlattice arrays detected and calculated by small angle X-ray diffraction (2.71 nm). Field emission scanning electron microscopy exhibited that L alpha-Cu(2)O presents granular particles of around 700 nm. In contrast, the template free Cu(2)O (TF-Cu(2)O) presents no ordered nanostructure and shows polyhedral morphology. The possible mechanism of SDS serving as soft template was proposed and discussed in thermodynamics.