Rechargeable Li–S batteries have received ever-increasing attention recently due to their high theoretical specific energy density, which is 3 to 5 times higher than that of Li ion batteries based on intercalation reactions. Li–S batteries may represent a next-generation energy storage system, particularly for large scale applications. The obstacles to realize this high energy density mainly include high internal resistance, self-discharge and rapid capacity fading on cycling. These challenges can be met to a large degree by designing novel sulfur electrodes with “smart” nanostructures. This highlight provides an overview of major developments of positive electrodes based on this concept.