<p>Extreme electron-ion non-equilibrium states, generated by ultrafast laser excitation, lead to melting processes that are fundamentally different from those under conventional thermal equilibrium and remain not fully understood. Through neural network-enhanced multiscale simulations of tungsten and gold nanofilms, we identify electronic pressure relaxation as critical to heterogeneous phase transformations. This nonthermal expansion generates a density decrease that enable surface-initiated melting far below equilibrium melting temperatures, creating electronic pressure-driven solid-liquid interface propagation at a high speed of 2500 ms⁻¹—tenfold faster than that of thermal heterogeneous melting mechanisms. Simulated time-resolved X-ray diffraction signatures distinguish this nonthermal expansion from thermal expansion dynamics driven by thermoelastic stress. These results establish hot-electron-mediated lattice destabilization as a universal pathway for laser-induced structural transformations, providing new insights for interpreting time-resolved experiments and controlling laser-matter interactions.</p>