We study the self-assembly dynamics of DLPE (dilauroyl-phosphatidylethanolamine) and DLPG (dilauroyl-phosphatidylglycerol) phospholipids bilayer in solution. DLPE is capable of forming inverse topological structures, suited for encapsulating hydrophobic drugs but is also known to have highly ordered crystalline structure at temperatures below 40°C. Previous studies showed that additional DLPG stabilize the lipid structures when designing drug delivery system. Using our in-house small and wide angle X-ray scattering system we measured the time-dependent structures of multi-lamellar vesicles (MLV) self-assembled from various DLPE:DLPG stoichiometries. We show that DLPE:DLPG mixtures at physiological conditions form a metastable liquid crystal phase for tens of hours, upon heating above 40°C and cooling back down to 37°C before transitioning back to the crystalline phase. Our results show that relaxation time and the transition time back to crystalline state are correlated and strongly depends on DLPE:DLPG ratio having a minimum around 95:5 (mol:mol %). We expect these results to be of high importance when designing drug-delivery vesicles having preset triggering mechanism for release upon crystallization.