Various hierarchical ZnO architectures constructed by twinned structures have been synthesized via a trisodium citrate assisted hydrothermal method on a large scale. The probable formation mechanisms of hierarchical ZnO structures with twinned structure were proposed and discussed. The hierarchical ZnO with twinned structures are composed of two hemispheres with a center concave junction to join them together at their waists. The ZnO microspheres with rough surfaces were obtained when the concentration of trisodium citrate is 0.1 M. However, the football-like microspheres consisted of hexagonal nanosheets were formed when adding glycerol into the water, which should be attributed to the slower nucleation and growth rate of nanocrystals. The hamburger-like ZnO with different aspect ratio and nonuniform ZnO microspheres were generated due to the different quantity of initial nuclei and growth units when simply modulating the concentration of trisodium citrate. The surface area of football-like ZnO is about 3.51 times of microspheres composed of irregular particles. However their photocatalytic performances are similar under UV light irradiation, which indicates that pore sizes of the sample have more important influences on the photocatalytic activity. (C) 2015 Elsevier B.V. All rights reserved.