The intriguing functionalities of halide perovskites have led to an extensive exploration of this material for sustainable optoelectronic applications. However, the inherent chemical complexities in the materials system result in uncontrolled chemical heterogeneities in the synthesized device-grade-level crystallites, which still compromises functionalities. Yet, this phenomenon remains poorly understood due to the massive chemical and synthesis spaces. Here, an innovative strategy based on a high-throughput automated experimental workflow will be introduced, which is designed to expedite the discovery of fundamental principles and optimal processing pathways in chemically complex perovskites. This workflow serves as a powerful tool for constructing detailed chemical maps of perovskite synthesis, empowering bespoke customization of their structures, dimensionalities, and functionalities. An outlook of the powerfulness of such automated experimental workflows in accelerating materials discoveries will be illustrated.