Copper oxyhydroxide (CuOOH), an unavoidable oxidic product of CuO and Cu(OH)₂ electrocatalysts, is always ignored in water splitting. In this work, we investigated the OER /ORR electrocatalytic activity of all CuOOH series (C2/m, Cmc2_1, and Pmn2₁) and proposed an improvement scheme for catalytic activity using the DFT method. The results showed that pure CuOOH matrixes with large OER/ORR overpotentials (${\eta }_{\text{OER}/\text{ORR}}$) were inert toward OER/ORR. Therefore, eleven metals (Mn, Fe, Co, Ni, Zn, Mo, Ru, Rh, Pd, W, and Ir) were used to activate the CuOOH substrates. It is found that the OER/ORR performances of all CuOOH series can be significantly improved by Co or Rh doping. Especially for 2D-layered C2/m-CuOOH substrate, the ${\eta }_{\text{OER}/\text{ORR}}$ was reduced from 1.26 V/2.01 V to 0.25 V/0.22 V and 0.36 V/0.46 V by Co and Rh embedding, respectively, which mainly owes to the regulation from the moderate d-orbital electrons of doped Co and Rh. This work systematically revealed the OER/ORR performance of the CuOOH series, which will promote the development of new catalysts and help us to deeply understand and improve the OER/ORR performance of previous copper oxide electrocatalysts.