Cr3+-doped LiInSiO4 phosphors were prepared by a solid-state reaction method. X-ray diffraction measurement was carried out for crystalline phase identification. Absorption, photoluminescence, excitation, and time-resolved spectra were measured to investigate the optical properties of the phosphors. Two broadband near-infrared emissions centered at 920 and 1172 nm were observed. Time-resolved spectra show that the emission at 1172 nm decays more quickly than the emission at 920 nm. The electron spin resonance spectra exhibit a broad resonance signal at g = 1.96 because of exchange-coupled Cr3+ pairs. The value of Dq/B for low and intermediate crystal fields was evaluated. We suggest that Cr3+ incorporated into different octahedral sites of the crystal is responsible for the different near-infrared luminescence.