Yttrium ferrite (YFeO3) is highly attractive as a promising multiferroic material and also has been proven to have potential in the field of near-infrared reflective cold pigments. In this work, YFeO3 powders were fabricated via metal citrate xerogel mediated molten salt procedure at different temperatures. The complexation process of the metal citrate xerogel as a precursor was promoted by the salt medium, and the molten salt medium reduces the reaction temperature to obtain morphologically distinctive YFeO3 without impurity. The orange YFeO3 powders possessed outstanding near-infrared reflection characteristics and high solar reflectance. The relationship of particle size, particle shape, charge state distribution, magnetic performance and near-infrared reflection performance of YFeO3 was investigated. Specifically, with the increase of calcining temperature, particle size increases, thereby increasing the infrared reflectivity. The rising in the amount of Fe2+–Fe3+ ion pairs increased the absorption of free carriers, thereby reducing the infrared reflectivity. The two factors contributed together to the near-infrared reflectivity, which first increased and then decreased with the increase of calcining temperature. In addition, the increase in the ratio of Fe2+ also hindered the super-exchange and Dzyaloshinskii–Moriya interaction of Fe–O–Fe, thereby improving of the weak-ferromagnetic behavior of YFeO3.