AbstractIncomplete transformations from ferromagnetic to charge ordered states in manganite perovskites lead to phase-separated microstructures showing colossal magnetoresistances. However, it is unclear whether electronic matter can show spontaneous separation into multiple phases distinct from the high temperature state. Here we show that paramagnetic CaFe₃O₅ undergoes separation into two phases with different electronic and spin orders below their joint magnetic transition at 302 K. One phase is charge, orbital and trimeron ordered similar to the ground state of magnetite, Fe₃O₄, while the other has Fe²⁺/Fe³⁺charge averaging. Lattice symmetry is unchanged but differing strains from the electronic orders probably drive the phase separation. Complex low symmetry materials like CaFe₃O₅ where charge can be redistributed between distinct cation sites offer possibilities for the generation and control of electronic phase separated nanostructures.