Hollow carbon spheres (HCS) with a nanoporous shell are promising for the use in lithium–sulfur batteries because of the large internal void offering space for sulfur and polysulfide storage and confinement. However, there is an ongoing discussion whetherthe cavity is accessible for sulfur. Yet no valid proof of cavity filling has been presented, mostly due to application of unsuitablehigh-vacuum methods for the analysis of sulfur distribution. Here we describe the distribution of sulfur in hollow carbon spheres bypowder X-ray diffraction and Raman spectroscopy along with results from scanning electron microscopy and nitrogen physisorption.The results of these methods lead to the conclusion that the cavity is not accessible for sulfur infiltration. Nevertheless, HCS/sulfur composite cathodes with areal sulfur loadings of 2.0 mg·cm−2 were investigated electrochemically, showing stable cyclingperformance with specific capacities of about 500 mAh·g−1 based on the mass of sulfur over 500 cycles.