In this work, the Li/Zn-doped near-infrared reflective inorganic blue pigment YIn 0.9−x Mn 0.1 M x O 3−δ (M = Li/ Zn, x = 0−0.4) was synthesized by the high-temperature solid-state reaction method. The phase structures, morphologies, color properties and optical properties of synthetic pigments were characterized by X-ray diffractometer (XRD), scanning electron microscope (SEM), CIE1976 color space system, UV−vis-NIR spectrophotometer, and other instruments. All the doped samples have a hexagonal structure with space group P63cm (185). Compared with YIn 0.9 Mn 0.1 O 3 (b* = −45.91), Li/Zn doped pigments have richer blue hues (b* is ranged from −29.59 to −55.14), which can meet the needs of public's demands for blue hues. The NIR solar reflectance (R*) of all the samples are above 70%, and the highest R* with different doping concentrations can reach 86% (M = Li, x = 0.2), which is about 16% higher than YIn 0.9 Mn 0.1 O 3 . YIn 0.9−x Mn 0.1 M x O 3−δ (M = Zn/Li, x = 0−0.4) are indicated to possess higher near-infrared solar reflectivity than other blue compounds, including commercial products. The surface temperature difference between the Li-doped (x = 0.2)/Zndoped (x = 0.1) paints and commercial ultramarine paint can reach about 20 and 10 °C, respectively. The above properties ensure the potential applications of environmentally friendly YIn 0.9−x Mn 0.1 M x O 3−δ pigments with a rich blue-hue in the field of energysaving materials.