Abstract A simple one-pot hydrothermal route has been demonstrated for the fabrication of 3D [email protected] zinc silicate (ZSO) core–shell nano-heterostructures on the Si substrate. Individual 3D [email protected] core–shell nano-heterostructures were assembled with many bundle-like branches, and each bundle-like branch was composed of the ZnO rod as the core and ZSO nanowires as the shell. The structure and composition of the 3D [email protected] nano-heterostructures could be varied with different reaction conditions and exhibit excellent reproducibility as well. In addition, a possible mechanism for the fabrication of 3D [email protected] nanohybrids was proposed, suggesting that heterogeneous nucleation played important roles in the formation of 3D nanostructures. The resultant 3D [email protected] nano-heterostructure films exhibited hydrophobic adhesive characteristic with a water contact angle of 142.1° and a high contact angle hysteresis, which held a great potential in surface wettability and other opto-electronic applications.