Perovskite-type La1-xCaxMnO3 (0.1 <= x <= 0.4) manganites with perfect crystallinity were synthesized by a sol-gel method and used as low-cost platinum-free counter electrodes (CEs) for dye-sensitized solar cell (DSSCs). It is found that the performance of the cells increases with the increase in x, the highest energy conversion efficiency being 6.46% when x = 0.3, which is up to 91.2% of Pt CE (7.08%). The phenomena can be ascribed to the improved conductivity of the system with Ca doping. Besides, the sol-gel method is more suitable for large-scale preparation compared to the solvothermal method and hydrothermal method. This work will open up a new way to explore CE materials for high efficiency and low cost DSSCs.