Abstract: A versatile hydrothermal strategy for the growth of a centimeter-sized CaO/amorphous carbon rope was introduced in this article. It is demonstrated that the centimeter-sized rope is composed of abundant amorphous carbon “belt” and “stick” with small polygonal CaO particles in the size of 3.0–5.0 nm embedded in the “belt” and “stick” framework. With the increase in NaOH amount, polygonal Ca(OH)2 particles in the size of 0.5–3.0 μm are found, instead of the CaO/amorphous carbon rope. This morphology evolution results from the competition of structure-directing and hydrothermal-carbonizing of organic agents during hydrothermal reaction. These results may give good suggestions for the controllable growth of newly unique morphological micro/nano architectures in solution phase reactions.