The electrochemistry, near-infrared photoluminescence (NIR-PL) spectroscopy, and electrogenerated chemiluminescence (ECL) of Au(25)(SC(2)H(4)Ph)(18)(+)C(6)F(5)CO(2)(-) (Au(25)(+)) clusters were investigated. For the first time, NIR-ECL emission was observed in both annihilation and coreactant paths. Our newly developed spooling spectroscopy was employed during the ECL evolution and devolution processes along with explicit NIR-PL spectroscopy to elucidate light generation mechanisms. It was discovered that the electronic relaxation of the Au(25)(-) excited state to the ground state plays a key role in giving off ECL at 893 nm, while intermediate, strong, and weak NIR-PL emissions at 719/820, 857, and 1080 nm can be attributed to the excited states higher than the HOMO-LUMO gap, across the HOMO-LUMO gap, and of semi-rings, respectively.