In the past few decades, the dependence of the people towards the biomaterial based products such as scaffolds and hydrogels are rapidly rises in the urbanization of industrial, cosmetics, denture and pharmaceutical activities. Biomaterials are the ideal alternative compared with diesel-based materials and it is arising up recently due to its attribute as environment friendly and biocompatible to human being. Poly(methyl methacrylate-co-methacrylic acid), PMMA-co-MAA is still a newly biomaterial where has not been fully utilized in colloidosomes production. In this study, a total of 9 samples which made up from 6 samples of Polycaprolactone, PCL with two different surfacants and 3 samples of PMMA-co-MAA produced were determined by their different parameters which are concentration of structural polymer, concentration of polymer surfactant and types of surfactants and physical characteristic (partical size and diameter). The results of proximate analysis of PCL showed a significant outcome in different polymer surfactants within the six samples whereas all of the parameters are remarkable different in the particle sizes within the 9 samples. For physical characteristics analysis, both of the factors were showed obviously different in concentration of structural polymer, concentration of polymer surfactant and types of surfactants. FESEM image proved the ability of PMMA-co-MAA as hollow colloidosomes where small colloids were present and partially fused on the surface of PMMA-co-MAA colloidosome surface. PMMA-co-MAA also a birefringent material as it gives interference colours when placed between crossed polarizers. The average diameter is 30.46 μm, 32.74 μm and 33.35 μm by the samples from PCL/PVA system which the concentration of PVA were 1.20%, 0.50% and 0.25% repectively. Whereas for the average diameter of hollow colloidosomes in PCL/SE system on concentration of sugar ester 1.20%, 0.50% and 0.25% were 2.663 μm, 4.700 μm and 7.940 μm. The average hollow colloidosome’ diameter for PMMA-co-MAA/PVA system was 31.68 μm with the structural polymer concentration of 3.00 wt% and 1.20% PVA as polymer surfactant. The concentration of PVA surfactant 1.20% in 1.50 wt% WT%PMMA-co-MAA/PVA systems that produced hollow colloidosomes with average diameter of 19.20 μm and the 0.25% PVA as polymer surfactant did not give any positive results. Based on the overall results, the average diameter and particle sizes of PMMA-co-MAA proved that it is suitable in synthesis hollow colloidosomes.