AbstractMetastability and phase coexistence are important concepts in colloidal science. Typically, the phase diagram of colloidal systems is considered at the equilibrium without the presence of an external field. However, several studies have reported phase transition under mechanical deformation. The reason behind phase coexistence under shear flow is not fully understood. Here, multilamellar vesicle (MLV)‐to‐sponge (L3) and MLV‐to‐Lα transitions upon increasing temperature are detected using flow small‐angle neutron scattering techniques. Coexistence of Lα and MLV phases at 40 °C under shear flow is detected by using flow NMR spectroscopy. The unusual rheological behavior observed by studying the lamellar phase of a non‐ionic surfactant is explained using 2H NMR and diffusion flow NMR spectroscopy with the coexistence of planar lamellar–multilamellar vesicles. Moreover, a dynamic phase diagram over a wide range of temperatures is proposed.