Template-free, one step formation of Cu(In, Ga)Se2 (CIGS) nanotip arrays (NTRs) to enhance device efficiency were discussed. Through Ar+ ion milling process, the CIGS NTRs could be formed directly on the CIGS layer. The angles and lengths of CIGS NTRs could be precisely controlled by incident angle of Ar+ beam and milling time, respectively. Mechanisms were proposed to be a self-masking effect by Cu segregation formed at early stage confirmed by Transmission Electron Microscopy, Grazing Incidence X-ray Diffraction, Energy Dispersive Spectroscopy, and Auger Electron Spectroscopy. Measurements of devices on various KCN washing time and thickness of CdS buffer layer were reported to achieve the highest efficiency of CIGS NTRs devices. This approach provides one-step fast process without templates, easy integration with in-line sputtering process, and no post-selenizatoin process for the formation of CIGS nanostructure, which can stimulate great attention not only in academic investigations but also in industrial side for practical applications.