Abstract Using density functional theory (DFT), we theoretically investigated the electronic and structural properties of monolayer and few-layer 2D materials obtained from the exfoliation of zinc-based layered hydroxide salts (LHSs). Four different compounds are investigated: Zn3(OH)4(NO3)2, Zn5(OH)8Cl2.H2O, Zn5(OH)8(NO3)2.2H2O and NaZn4(OH)6SO4Cl.6H2O. We found exfoliation energies in the range of 30 meV/A2 for all cases. Monolayer structures remained semiconducting like the respective bulk compounds, although in some cases, the band gap changes its character from indirect to direct. We also explored the effects of dehydration, which can also change the gap character from indirect to direct in some monolayer structures. Finally, we found that the anion or cation removal from the interlayer region can turn the monolayer systems into metallic, by means of electron and hole doping, respectively.