AbstractAs zero‐emission technologies, a daytime radiative cooling (RC) strategy developed recently, and photovoltaic (PV) and thermoelectric (TE) technologies have aroused great interest to reduce fossil fuel consumption and carbon emissions. How to integrate these state‐of‐the‐art technologies to maximise clean electricity from the sun and space remains a huge challenge, and the limit efficiency is still unclear. In this study, a spectral‐splitting PV‐TE hybrid system integrated with RC is proposed to maximise clean electricity from the sun and space without any emissions. For the sun acting as a typical constant heat‐flux heat source, the current thermoelectric theory overestimates the thermoelectric efficiency highly since the theory is based on constant temperature‐difference conditions. A new theory based on heat‐flux conditions is employed to achieve maximum thermoelectric efficiency. The PV‐TE hybrid system with RC is superior to the conventional hybrid system, not only in terms of higher efficiency but also in its 24‐h operation capacity. In a system with a single‐junction cell, the total efficiency with 30 suns (39.4%) is higher than the theoretical PV efficiency at 500 suns (38.2%). In a hybrid system with four‐junction cells, total efficiency is over 65% which is superior to most current photoelectric and thermal power systems.