In this work, hierarchical flowerlike Bi2S3 structures constructed by polycrystalline nanoplates combined with urchinlike and wirelike Bi2S3 were synthesized by using a thioglycolic acid assisted solvothermal method. On the basis of the time-dependent experimental results, an anion exchange process and a self-assembly mechanism were proposed to account for the growth mechanism of the synthesized flowerlike Bi2S3. In addition, the morphology and the crystalline nature of the products can be easily tuned by changing the reaction temperature. Moreover, the electrochemical properties (electrochemical hydrogen-storage and lithium-intercalation performance) of the products were studied. The flowerlike Bi2S3 possesses both higher electrochemical properties and better cycle stabilities compared to urchinlike and wirelike Bi2S3.