The self-assembly and self-organisation of amphiphilic molecules led the formation of limiting boundary structure around protocell-like entities. The primitive selective permeability property of membrane compartment increased the complexity of metabolic network and internal structure. If these metabolites are not quickly used in subsequent reactions they would leak into the environment. The 1:2:1:1 Jeewanu mixture (Bahadur and Ranganayaki 1970) shows the photochemical formation of self-sustaining, autoreplicative protocell-like microstructures “Jeewanu”. Jeewanu have distinct structural organization and are able to show some properties of biological orders viz. growth from within and multiplication by budding. They have distinct double walled limiting boundary. The histochemical characterization shows the presence of some compounds of biological interest and enzyme-like activities. The present investigations shows that only water molecules cross the limiting boundary structure of Jeewanu except other organic solvents. These findings shows the emergence of primitive selective property in limiting boundary structure of Jeewanu. The permeability property plays a pivotal role in sustaining, auto replicative and quasi-metabolic behavior of protocell-like structure. The findings contribute to our understanding of how early prebiotic structures may have acquired essential cellular properties and offer new perspectives in the study of artificial life and synthetic biology. These findings shows the emergence of primitive selective property in limiting boundary structure and also support the “Metabolic First” theory.