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Abstract Synthesizing intermetallic phases containing noble metals often poses a challenge as the melting points of noble metals often exceed the boiling point of bismuth (1560 °C). Reactions in the solid state generally circumvent this issue but are extremely time consuming. A convenient method to overcome these obstacles is the co‐reduction of metal salts in polyols, which can be performed within hours at moderate temperatures and even allows access to metastable phases. However, little attention has been paid to the formation mechanisms of intermetallic particles in polyol reductions. Identifying crucial reaction parameters and finding patterns are key factors to enable targeted syntheses and product design. Here, we chose metastable γ‐BiPd as an example to investigate the formation mechanism from mixtures of metal salts in ethylene glycol and to determine critical factors for phase formation. The reaction was also monitored by in situ X‐ray diffraction using synchrotron radiation. Products, intermediates and solutions were characterized by (in situ) X‐ray diffraction, electron microscopy, and UV‐Vis spectroscopy. In the first step of the reaction, elemental palladium precipitates. Increasing temperature induces the reduction of bismuth cations and the subsequent rapid incorporation of bismuth into the palladium cores, yielding the γ‐BiPd phase.