Near-infrared (NIR) light has been widely used in fields, such as biometrics recognition, security monitoring, lighting for indoor agriculture, food safety inspection and biomedical imaging. NIR phosphors are crucial components for NIR phosphor-conversion light-emitting diodes (NIR pc-LED). Compared with the traditional high-temperature solid phase method for spinel-type phosphors, the synthesis by the sol-gel combustion method is rapid, more efficient, and requires lower temperatures, with good homogeneity and uniformed nano-size particle. Here we report the synthesis of a panel of NIR phosphors that are composed of nano-sized Ni2+-doped MgAl2-xGaxO4 solid-solution of spinal crystals with high phase purity. By adjusting the ratios of Al/Ga, the Ni2+-doped phosphors with spinel (MgAl2O4) to hybrid-spinel (MgGa2O4) crystal structures were obtained. The phosphor with the Al/Ga ratio of 0.8–1.2 showed the maximal NIR emission intensity, which was 5.9 times higher than that of the MgAl2O4 spinel structure, with an internal photoluminescence quantum efficiency of 31.63 %. The phase transformation of the crystal form from spinel to hybrid-spinel resulted in a shift of the emission peak from 1223 nm to 1287 nm, realizing a ∼ 64 nm structure-dependent tunability of NIR luminescence. We assembled a NIR pc-LED device using the optimal phosphor and a commercially available near ultraviolet LED, and experimentally demonstrated its application for night-vision monitoring and bioimaging of veins in a human hand.