This study reports a simple method for the controlled synthesis of uniformly shaped carbon hollow structures by an ethanol-assisted thermolysis of zinc acetate. The experimental evidence reveals that the generated zinc oxide nanostructures act as in-situ templates to form the carbon hollow structures. The morphologies, including the shell thickness, cavity size, and aspect ratio, can be controlled by the reaction time and the heating procedure, and hollow nanospheres, nanocapsules, nanorods, and microtubes can be obtained. Experimental results show that the as-synthesized carbon hollow structures exhibit excellent thermal and structural stability to temperatures as high as 1200 °C.