Exploratory synthesis of solids is essential for the advancement of materials science but is also highly time- and resource-intensive. Here, we demonstrate an efficient strategy to explore solid-state synthesis of quaternary cesium chlorides in the search space of CsnAIBCl6 (n = 2 or 3, A = Li, Na or K, and B = d or p-block metal), where the target compositions are selected from a pool of candidates based on computationally predicted stabilities and availability of viable precursor powders. Synthesizability of the targets is assessed by observing the evolution of starting phases upon heating under in situ synchrotron X-ray diffraction. Laboratory synthesis is attempted for promising targets, and resulting materials are characterized by powder X-ray and neutron diffraction and subsequent Rietveld refinement. We focus on how computational predictions can be bridged to experimental characterizations in exploratory synthesis and report on successful and failed synthesis attempts for compounds of type Cs2AIBIIICl6, revealing underexplored variants including new polymorphs of Cs2LiCrCl6 and Cs2LiRuCl6, and a new compound Cs2LiIrCl6.