The planets and larger rocky bodies of the inner solar system are differentiated, and consist of metallic, iron-rich cores surrounded by thick shells of silicate. Core formation in these bodies, i.e. the segregation of metal from silicate, was a key process in the early solar system, and one which left a lasting geochemical signature. It is commonly assumed that extensive silicate melting and formation of deep magma oceans was required to initiate core formation, due to the inability of iron-rich melts to segregate from a solid silicate matrix. Here we assess the role of deformation in aiding segregation of core-forming melts from solid silicate under conditions of planetary deep interiors. Low-strain rate, high-pressure/temperature deformation experiments and high-resolution 2-D and 3-D textural analysis demonstrate that deformation fundamentally alters iron-rich melt geometry, promoting wetting of silicate grain boundaries and formation of extensive micron to sub-micron width Fe-rich melt bands. Deformation–aided Fe-S melt networks noted here contrast those observed in higher finite strain experiments conducted at lower pressure, and may reveal either an alternative mechanism for melt segregation at higher pressures, or an early stage process of melt segregation. Results suggest, however, that core-mantle chemical equilibration cannot be assumed in models of planetary formation, and that instead, the chemistry of rocky planets may record a complex, multi-stage process of core formation.