Abstract: The Cu-doped ZnO twinned structure materials with hexagonal prism morphology were synthesized by direct precipitation and the effects of Cu2+ ion on the formation of twinned structure and morphology were investigated. With the increase of Cu2+ concentration in reaction solution the particle sizes of as-prepared ZnO materials increased following the change of morphologies from slender rod to stumpy hexagonal prism and the decrease of length-diameter ratios from 10:1 to 1.2:1. The tubular Cu-doped ZnO materials were obtained via corroding process by concentrated aqueous alkali and the formation mechanism was proposed. The photoluminescence properties of Zn(Cu)O materials were studied and the Cu-doped ZnO showed broad and strong green emission at 520 nm, attributed to the transition of copper ion between Cu2+ and Cu+ in interior of ZnO crystal. The formation of tubular construction enhance the intensity of green emission.