Amid burgeoning environmental concerns, electrochemical energy storage has rapidly gained momentum. Among the contenders in the ‘beyond lithium’ energy storage arena, the lithium–sulfur (Li–S) battery has emerged as particularly promising, owing to its potential to reversibly store considerable electrical energy at low cost. Whether or not Li–S energy storage will be able to fulfil this potential depends on simultaneously solving many aspects of its underlying conversion chemistry. Here, we review recent developments in tackling the dissolution of polysulfides — a fundamental problem in Li–S batteries — focusing on both experimental and computational approaches to tailor the chemical interactions between the sulfur host materials and polysulfides. We also discuss smart cathode architectures enabled by recent materials engineering, especially for high areal sulfur loading, as well as innovative electrolyte design to control the solubility of polysulfides. Key factors that allow long-life and high-loading Li–S batteries are summarized.