Hierarchical assembly of hollow microstructures is of great scientific and practical value and remains a great challenge. This paper presents a facile and one‐pot synthesis of Cu2O microspheres with multilayered and porous shells, which were organized by nanocrystals. The time‐dependent experiments revealed a two‐step organization process, in which hollow microspheres of Cu2(OH)3NO3 were formed first due to the Ostwald ripening and then reduced by glutamic acid, the resultant Cu2O nanocrystals were deposited on the hollow intermediate microspheres and organized into finally multishell structures. The special microstructures actually recorded the evolution process of materials morphologies and microstructures in space and time scales, implying an intermediate‐templating route, which is important for understanding and fabricating complex architectures. The Cu2O microspheres obtained were used to fabricate a gas sensor, which showed much higher sensitivity than solid Cu2O microspheres.

Ni(OH)2 hollow microspheres with beta-Ni(OH)2 nanosheets as the in situ formed building units were fabricated via a novel template-free approach in a strong alkaline solution of glycine, and can be converted into NiO hollow microspheres by a thermal decomposition process.

Morphologies of hydroxyapatite with partial substitution of fluorine (FHAp) have been finely modulated from prickly spheres, whisk brooms, flowers, dandelions, and nanofibers to ultralong nanoribbons through altering the reaction conditions and adding glutamic acid. X-ray diffraction, high-resolution transmission electron microscopy, energy-dispersive X-ray spectroscopy, and so forth were performed for characterizing the resultant powders and analyzing the growth process. Condition experiments were compared comprehensively and revealed that FHAp crystals with various morphologies were formed, generally, through a fractal growth process of double splitting.

In this work, various TiO 2 hollow structures, such as pseudocubes, ellipsoids, capsules and peanuts, have been synthesized through the following process: hydrothermal deposition of anatase TiO 2 on monodisperse Fe 2 O 3 microscale particles with different shapes (pseudocubes, ellipsoids, capsules and peanuts) and the sequential acid-dissolution of the Fe 2 O 3 cores. The morphologies of these TiO 2 hollow structures are similar to their Fe 2 O 3 templates. When all the obtained hollow TiO 2 structures are used as the anode material for lithium-ion batteries, they show higher discharge capacity as compared to TiO 2 solid microspheres.