We synthesized octapod Cu-Au bimetallic alloy with a concave structure by employing a replacement reaction between AuPPh3Cl and Cu nanocubes. Using the Cu nanocube as sacrificial templates, we have successfully generated high-active sites on alloy nanocrystals by carefully tuning the replacement reaction and growth. The key is to afford the proper concentration of AuPPh3Cl-TOP to the reaction solution. When the Au precursor with high concentration is injected into the galvanic replacement reaction, the growth dominated the process and hollowed octapod Cu-Au alloy was obtained. In contrast, when the concentration of the Au precursor is low, the replacement reaction can only take place at the nanocrystals, leading to generate Cu-Au nanocages. This work provides an effective strategy for the preparation of hollow bimetallic nanocrystals with high-active sites.