In this work, novel MoS₂/nitrogen-doped carbon shell–core microspheres (MNCS) have been designed and prepared through the microwave-assisted method, and used as counter electrodes for platinum-free dye-sensitized solar cells (DSSCs). The results show that as-prepared shell–core composite microspheres possess low charge transfer resistance and high electrocatalytic activity. When used as a counter electrode for DSSCs, the powder conversion efficiency of an as-prepared cell with optimized MNCS reaches 6.2% under standard light illumination, which is comparable to cells with a conventional Pt counter electrode.