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Abstract Here, the combination of theoretical computations followed by rapid experimental screening and in situ diffraction studies is demonstrated as a powerful strategy for novel compounds discovery. When applied for the previously “empty” Na−Zn−Bi system, such an approach led to four novel phases. The compositional space of this system was rapidly screened via the hydride route method and the theoretically predicted NaZnBi (PbClF type,P4/nmm) and Na₁₁Zn₂Bi₅(Na₁₁Cd₂Sb₅type,P) phases were successfully synthesized, while other computationally generated compounds on the list were rejected. In addition, single crystal X‐ray diffraction studies of NaZnBi indicate minor deviations from the stoichiometric 1 : 1 : 1 molar ratio. As a result, two isostructural (PbClF type,P4/nmm) Zn‐deficient phases with similar compositions, but distinctly different unit cell parameters were discovered. The vacancies on Zn sites and unit cell expansion were rationalized from bonding analysis using electronic structure calculations on stoichiometric “NaZnBi”.In‐situsynchrotron powder X‐ray diffraction studies shed light on complex equilibria in the Na−Zn−Bi system at elevated temperatures. In particular, the high‐temperature polymorphHT‐Na₃Bi (BiF₃type,Fmm) was obtained as a product of Na₁₁Zn₂Bi₅decomposition above 611 K.HT‐Na₃Bi cannot be stabilized at room temperature by quenching, and this type of structure was earlier observed in the high‐pressure polymorphHP‐Na₃Bi above 0.5 GPa. The aforementioned approach of predictive synthesis can be extended to other multinary systems.