The current small-scale synthesis and relatively large size of Cu 2 O have limited its practical applications. Herein, we developed a hydrolysis strategy to prepare phase-pure Cu 2 O networks composed of small granules (ca. 25 nm) on a gram scale. The preparation involves in situ hydrolyzing the H x [Cu x Cl 2x ] complexes prereduced in N,N′-dimethylformamide (DMF). The DMF-soluble H x [Cu x Cl 2x ] complexes are critical for the homogeneous nucleation of CuCl seeds and subsequent hydrolysis, allowing for separate control over the nucleation and growth stages to regulate the formation of Cu 2 O networks. The novel Cu 2 O networks possess numerous exposed active sites and hierarchical porosities, conferring high catalytic activity and fast mass transfer capability. The inherent peroxidase-mimic activity of Cu 2 O is severely inhibited under neutral conditions but can be triggered by Cr 6+ , enabling the colorimetric assay of Cr 6+ with the assistance of the oxidation-induced color change of 3,3′,5,5′tetramethylbenzidine. Through density functional theory calculation, we confirmed that the attachment of Cr 6+ on the Cu 2 O surface reduced the dissociation energy of H 2 O 2 , enhancing the enzyme-mimic activity. The colorimetric detection method demonstrated a sensitive and specific assay capability for Cr 6+ (LOD = 0.095 μM). Our work offers a straightforward protocol for novel design of metal or metal-based nanomaterials for nanozymes or other applications.