<p>The structure of a polymer determines the characteristics and final properties of a polymer. Isotactic, syndiotactic, and atactic are different forms of tacticity that can affect the properties of the polymer. Most energetic polymers usually have different tacticities that can change their properties from one form to another. In this research, the compatibility of polyglycidyl nitrate as an energetic polymer with nitrate ester plasticizers such as triethylene glycol dinitrate (TEGDN), 1,2,4-butanetriol trinitrate (BTTN), trimethylolethane trinitrate (TMETN), and glyceryl trinitrate (GTN) was studied by NPT-molecular dynamics (NPT-MD) simulation and Compass III forcefield settings. For this purpose, the compatibility of isotactic, syndiotactic, and atactic forms with TEGDN, BTTN, TMETM, and GTN plasticizers was simulated by balancing different parameters such as temperature, density, energy, etc. Molecular dynamics simulations showed that the isotactic form of polyglycidyl nitrate has the highest binding energy and compatibility with these plasticizers, and syndiotactic and atactic forms are not suitable for the compatibility of these plasticizers. Among the studied plasticizers, the highest binding energy of 385.304&#xa0;kcal.mol^− 1 was observed in BTTN with isotactic polyglycidyl nitrate, and BTTN showed the most compatibility with isotactic polyglycidyl nitrate. The analysis of the solubility parameter, radial distribution function (RDF), and calculated mechanical properties demonstrated that BTTN exhibits excellent miscibility and compatibility with isotactic-polyglycidyl nitrate.</p>