Maintaining the intrinsic features of mesophases is critically important when employing phospholipid self-assemblies to mimic biomembranes. Inorganic solid surfaces provide platforms to support, guide, and analyze organic self-assemblies but impose upon them a tendency to form well-ordered phases not often found in biomembranes. To address this, we measured mesophase formation in a thiolate self-assembled monolayer (SAM) of diacyl phospholipid, 1,2-dipalmitoyl-sn-glycero-3-phosphothioethanol (DPPTE) on Au(111), and provide thermodynamic analysis on the mixing behavior of inequivalent DPPTE acyl chains. Our work has uncovered three fundamental issues that enable mesophase formation: (1) Elimination of templating effects of the solid surface, (2) Weakening intermolecular and molecule-substrate interactions in adsorbates, and (3) Equilibrium through entropy-driven self-assembly. Thus, our work provides a more holistic understanding of phase behavior, from liquid phases to mesophases to highly crystalline phases, in organic self-assemblies on solid surfaces, which may extend their applications in nanodevices and to the wider fields of biology and medicine.