Concentrating photovoltaic–thermoelectric (CPV–TE) coupling system is an efficient solar‐to‐electric technology, but the nonuniform illumination and temperature caused by the concentrated light have a significant impact on the power generation performance of the cell. This work improves the intensity distribution through the self‐made birefringent prism, and further studies the effect of uniform or nonuniform illumination on the power generation performance of CPV–TE system under different light intensities and cooling conditions. The results show that the output power of PV cell at uniform illumination can achieve 14.74% higher than that at nonuniform illumination due to the decline of cell’ surface temperature difference. Meanwhile, the cooling condition can further enhance the output power of PV or TE cell, and weakens the impact of the illumination nonuniformity on the power generation performance of PV cell. Through the joint optimization of uniform illumination and 10 °C cooling condition, CPV–TE coupling system increases the output power by 15.83% at 10 kW m−2. TE device can further enhance the output power by 46.09 mW through the thermoelectric conversion. Surprisingly, the environmental cost from CPV–TE system reduces carbon dioxide emission of 26471.01¥ m−2 every day. The outdoor CPV–TE coupling system has a certain assistance for the practical development.