Acetate ester compounds find widespread use in various applications such as surface coatings, ink formulations, pharmaceuticals, and adhesives. It is essential to investigate the phase transition behavior of amyl acetate, amyl acetoacetate, and isoamyl acetoacetate in high-pressure supercritical CO2 (SC-CO2). The vapor-liquid equilibria (VLE) of the SC-CO2 + amyl acetate, SC-CO2 + amyl acetoacetate, and SC-CO2 + isoamyl acetoacetate systems were examined at different temperatures (313.2 ≤ T ≤ 393.2 K) and pressures (1.67 ≤ P ≤ 20.76 MPa). The solubility curve of these systems shows Type-I phase behavior, and the critical points of these binary mixtures were observed between the critical properties of the pure components involved in the systems. The solubility of amyl acetate, amyl acetoacetate, and isoamyl acetoacetate in the SC-CO2 + amyl acetate, SC-CO2 + amyl acetoacetate, and SC-CO2 + isoamyl acetoacetate systems increases with increasing temperature at constant pressure. The two-parameter model of Peng-Robinson equation of state along with a mixing rule, accurately correlated the phase transition behavior and critical mixtures curves for all three systems. The binary interaction parameters (BIPs) were adjusted, and the minimum root mean square deviation percentage was identified for all three systems. The calculated error% was found to be within reasonable limits, with values of 4.95 %, 3.93 %, and 4.18 % for SC-CO2 + amyl acetate, SC-CO2 + amyl acetoacetate, and SC-CO2 + isoamyl acetoacetate systems, respectively. Furthermore, the interaction parameters for the SC-CO2 + amyl acetoacetate mixture was found to be temperature-dependent, and the tested linear regression correlation coefficient for the BIPs parameters of (kij) and (ηij) are 0.98533 and 0.99083, respectively. This is the first research study on the phase behavior of acetate ester compounds in SC-CO2 solvents, and the results have a significant impact on industries at different operating conditions.