Nanoporous PdCu alloys (NP-PdCu) with uniform PdCu alloy ligament (~ 6 nm) and predetermined bimetallic ratio are prepared by selectively dealloying PdCuAl ternary alloys in an alkaline solution. NP-PdCu exhibit greatly enhanced electrocatalytic activity for formic acid and methanol oxidation compared with nanoporous Pd (NP-Pd). Moreover, the structure stability of NP-PdCu is also greatly enhanced. The electrochemical surface area of NP-PdCu is well-maintained after 10,000 potential cycles from 0.6 to 0.9 V (vs. RHE) in 0.5 M H 2SO 4 aqueous solution, while that of NP-Pd drops dramatically after 5000 cycles. The NP-PdCu will be promising anode catalysts for fuel cell-related technology. ► The nanoporous PdCu alloys show much improved electrocatalytic activities for small organic molecules oxidation compared with nanoporous pure Pd. ► The nanoporous alloys can reduce the amount of the used noble Pd. ► The nanoporous PdCu alloys show much improved structure stability compared with nanoporous Pd.