Abstract Enhancing the photoelectric conversion efficiency of on-chip solar cells is crucial for advancing solar energy harvesting in self-powered smart microsensors for Internet of Things applications. Here we show that adopting a center electrode (CE) layout instead of a ring electrode (RE) effectively reduces the shadowing effect of surface electrodes. Using a standard 0.18 μm CMOS process, we fabricated a 0.01 mm² segmented triple-well on-chip solar cell with CEs and highly doped interconnections. Measurements demonstrate a photoelectric conversion efficiency of 25.79% under solar simulator illumination, a 17.49% improvement over conventional designs. This on-chip solar cell is used for on-chip energy harvesting, achieving a maximum end-to-end conversion efficiency of 10.20%, referring to the overall efficiency from incident light power to load power output. The proposed energy harvesting system reliably provides a stable 1 V output to the load, even under varying illumination and load conditions.