This paper presents a comprehensive optimization strategy for the synthesis of new black ceramic pigments with low cobalt content while maintaining a single-phase spinel structure. The aim is to achieve comparable hues to those of an industrial benchmark containing five transition metals while minimizing the environmental impact. Exploring all possible compositions deriving from a five–component system (Cr, Mn, Fe, Co and Ni), through traditional methods would be extremely time consuming to guarantee an efficient sampling, requiring high experimental efforts. Hence, to identify the best black compositions, we employed a chemometric approach, the Design of Experiments, aiming to investigate the compositional domain derived by varying the metals stoichiometry within fixed boundaries to identify optimal pigment compositions. The resulting pigments (comprising Cr, Fe and Co), despite the lower cobalt content, exhibited optimal colorimetric properties comparable to the standard benchmark, with experimental ΔE values comparable to the ones predicted by the model. In particular, the pure spinels Cr1.05Fe1.05Co0.9O4 and Cr1.2Fe1.05Co0.75O4 displayed low lightness and chroma (L∗ = 2.4; C∗ = 5 and L∗ = 1.12; C∗ = 1.1, respectively), providing deep and dark black tonality. These compositions exhibit promising colorimetric performance and chemical stability, offering potential benefits for industrial applications.