Black pigments are very commonly used and arouse widespread interest in the ceramic industry. Nevertheless, these pigments contain toxic elements that are detrimental to human health. In view of this, the present work is focused on the development of sustainable black pigments prepared by a coprecipitation method at 1200 °C. Samples with the nominal formula (Gd_1–xCa_x)(Fe_0.95Zn_0.05)O_2.975–x/2 (x = 0.00, 0.05, 0.10) showed single-phase orthorhombic perovskite. The presence of dopants played an important role in the reduction of Fe³⁺ to Fe²⁺ and caused different local distortions in the structure which explained the final black colouration of these pigments in comparison with the red GdFeO₃ sample. The loss of symmetry and the increase in the number of d-d transitions of iron may explain the aforementioned changes. Co-doped pigments reached low C* values, improving on the purest black colour obtained in a commercial black ceramic pigment, which contains toxic elements. In addition to presenting good NIR solar reflectance values of up to 8%, the final colours of these pigments were also stable after their application in a commercial transparent glaze at 1080 °C that could be used for tiles.