A micro/nano-structure fabrication method is developed using focused ion beam implantation (FIBI) and FIB XeF2 gas-assisted etching (FIB-GAE). Firstly, the FIB parameters' influence on the FIBI depth is studied by SEM observation of the FIBI cross-section cutting by FIB. Nanoparticles with 10–15 nm diameter are found to be evenly distributed in the FIBI layer, which can serve as a XeF2-assisted etching mask when the ion dose is larger than 1.4 × 1017 ions cm−2. The FIBI layers being used as the etching mask for the subsequent FIB-GAE process are explored to create different micro/nano-structures such as nano-gratings, nano-electrode and sinusoidal microstructures. It is found that the method of combining FIBI with subsequent FIB-GAE is efficient and flexible in micro/nano-structuring, and it can effectively remove the redeposition effect compared with the FIB milling method.