Three-dimensional zinc hydroxide/dodecyl sulfate (Zn(OH) 2/DS) nanostructures self-assembled by nanolayers have been fabricated by pulsed laser ablation of bulk Zn in ethanol–water solution of sodium DS. The presence of ethanol causes defects in the hydroxyl group sites of Zn(OH) 2 that partially form ZnO structures, which facilitate heterogeneous nucleation of secondary nanolayers, resulting in three-dimensional nanostructures. These results demonstrate that laser ablation in liquid can be used to fabricate complex nanostructures by controlling the nucleation and growth behavior of laser-produced species.