A novel thermal deposition method was developed to coat Ca(OH)2 on the surface of nanoscale zero-valent iron (nZVI). The nZVI particles with the Ca(OH)2 coating layer, nZVI/Ca(OH)2, had a clear core-shell structure based on the transmission electron microscopy observations, and the Ca(OH)2 shell was identified as an amorphous phase. The Ca(OH)2 coating shell would not only function as an effective protection layer for nZVI but also improve the mobility of nZVI in porous media for its use in environmental decontamination. A 10% Ca/Fe mass ratio was found to result in a proper thickness of the Ca(OH)2 shell on the nZVI surface. Based on the filtration tests in sand columns, the Ca(OH)2-based surface coating could greatly improve the mobility and transport of nZVI particles in porous media. In addition, batch experiments were conducted to evaluate the reactivity of Ca(OH)2-coated nZVI particles for the reduction of Cr(VI) and its removal from water.