The properties of near-infrared (NIR) photoluminescence (PL) spectra in a range of 0.8–2.8 μm in fast neutron-irradiated α-Al2O3 are reported. Anomalous temperature dependence of NIR PL spectra was observed in neutron-irradiated α-Al2O3 for the first time. Highest PL intensity was measured at 260 K whereas the intensity at low temperatures below 220 K decreased significantly. Phonon-assisted indirect radiative recombination may be responsible for PL intensity enhancement at near room temperature. NIR PL band in a range of 0.8–2.8 μm may be well suited for application in broadly tunable color-center laser because of its enhanced PL intensity at near room temperature.