The microstructure in the electroformed copper liners of shaped charges prepared with different electrolytes was studied by Scanning Electron Microscopy (SEM) and Electron Backscattering Kikuchi Pattern (EBSP) methods. SEM observations revealed the existence of columnar grains in electroformed copper liners of shaped charges formed by electrolyte without any additive and the average grain size is about 3 μm. When an additive is introduced to the electrolyte, the grains formed in the copper liners become equiaxed and finer. EBSP results show that the columnar grain grown during electroformation has the most preferential growth direction, whereas a micro-texture does not exit in the specimen prepared by electrolyte with the additive. Further, explosive detonation deformation experiments show that penetration depth is dramatically improved when the electroformed copper liners of shaped charges exhibit equiaxed grains.