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A novel monolithic tree-branch-like copper-manganese oxides nanoarrays have been fabricated, exhibiting excellent periodate activation efficiency for the degradation of organic pollutants by synergistic effect between reduced copper and mixed-valence manganese species. [Display omitted] • A novel monolithic tree-branch-like copper-manganese oxides nanoarrays (CMM) was fabricated. • The Fenton-like microreactor CMM exhibits excellent catalytic activity for degradation of organic pollutants. • O 2 −, 1O 2 and OH were the major reactive radicals for 4-CP degradation in the CMM/NaIO 4 system. • The positive synergistic effect between reduced copper and mixed-valence manganese species for IO 4 - activation. Recently, considerable attention has been paid to develop novel Fenton-like oxidation systems for environmental remediation. The activation of periodate (NaIO 4) is a desirable oxidation process that drive redox reactions to produce abundant reactive oxygen species (ROS) by a suitable activator. This study reports a simple hydrothermal-calcination route for forming novel tree-branch-like copper-manganese oxides (CuMnO x @MnO x , CMM) nanoarrays, and the production of radical species from NaIO 4 induced by CMM for the removal of rhodamine B and 4-chlorophenol from wastewater. The synergistic effects of Cu oxides and Mn oxides composite significantly elevated the activation of periodate, exhibited excellent degradation performance in the CMM/NaIO 4. Furthermore, reduced copper species and mixed-valence manganese species play a major role in reaction via XPS analysis. Additionally, the underlying degradation mechanism of this work was systematically researched by radical quenching tests and EPR analysis. Superoxide anion radical (O 2 −) was the major free radicals in this system, simultaneously the production of non-radical singlet oxygen (1O 2) via the electron transfer, which are contributed to remove organic pollutants. This work provides a facile way for fabricating monolithic multi-component metal oxides, and new insights into understand activation mechanism of manganese-based periodate activator. [ABSTRACT FROM AUTHOR]