The present paper focuses on developing an optimised strength-conductive alloy in Cu–Fe–Si system. We present the effect of a cost-effective rapid-casting route on modifying the microstructure. The non-equilibrium phase transformation events are tracked and the evolution sequences of metastable phases in the microstructure are elucidated. The metastable phase transformation of the precipitates from DO19- to L12-ordered structure and its role in enhancing thermal conductivity are presented. A density functional theory (DFT)-based calculation also complements the experimental evidence of the relative stability of the evolved metastable phases. One of the key findings is the evolution of L12-ordered precipitates via face centred cubic (FCC)-based interfacial matrix template.