Nanomaterials that are enclosed by high index, reactive facets exhibit a significantly enhanced chemical reactivity, leading to superior performances in electronics, photonics, energy conversion and storage, as well as interfacing with living cells for various biological purposes. This article investigates the formation of single crystalline rare earth hydroxide nanobelts with selective control of high energy surfaces. Combining experimental and theoretical efforts, a carboxylic group and carbon–carbon double bond of oleic acid molecules are found to reduce the (0001) surface energy by 60%, leading to the growth of nanobelts and the stabilization of their high energy surfaces. These findings shed light on the growth of one-dimensional nanostructures that exhibit a simultaneous control over the crystallographic facets, shapes, and sizes. Our results engender a versatile synthesis method for nanomaterials that exhibit enhanced physical and chemical properties by overcoming their energy barrier to grow with high energy surfaces.