In this work, La0.5Sr0.5CoO3 (LSCO) perovskite oxide with perfect crystallinity was successfully synthesized via a sol–gel method and then used as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs). The DSSCs with LSCO CEs exhibited excellent electrocatalytic activity for the triiodide reduction and yielded a power conversion efficiency of 7.17%, which is greater than that of the Pt electrode (7.06%). Compared with the hydrothermal method and solvothermal method, sol–gel method is more suitable for large scale preparation. This work should open up a new class of CE materials for low-cost and high-efficiency DSSCs.