This study focused on creating tetraethylenepentamine (TEPA) modified copper hydroxyl phosphate (Cu2(OH)PO4) adsorbents via physical impregnation. The TEPA-modified Cu2(OH)PO4 adsorbents were analyzed for structure and characteristics through SEM, XPS, TGA, N2 adsorption–desorption studies. The effects of different parameters (TEPA contents, temperatures, flow rates and CO2 concentrations) and cyclic stability were evaluated. Kinetics, thermodynamics and density functional theory (DFT) calculations were employed to understand the impact of TEPA modification on Cu2(OH)PO4 for CO2 adsorption. Experimental results showed that a 50 wt% loading yielded optimal results, with a maximum surface area of 65.12 m2/g, a pore volume of 0.29 cm3/g, and a maximum adsorption capacity of 6.54 mmol/g. The amine efficiency is extraordinary which reached 67 %. The best performance occurred at 60 °C, 30 ml/min gas flow, and 15 vol% CO2 concentration. The pseudo-second-order kinetic model better described the CO2 adsorption process. The adsorption process was found to be exothermic at 20–60 °C and endothermic at 60–80 °C, suggesting physical–chemical co-adsorption and chemical adsorption, respectively. The adsorption activation energy is 34.322 kJ/mol. The DFT shows the adsorption energy ranged from −0.565 eV to −5.584 eV, indicating coexistence of physical and chemical adsorption. The d-band theoretical calculation shows that TEPA doping is beneficial to the adsorption of CO2 by Cu2(OH)PO4. Minimal structural modification of the adsorbate was observed, with bond lengths changing by less than 1 %. The density of states (DOS) curve shifted toward lower-energy states after adsorption, suggesting a more stable structural configuration post-adsorption. We have proved that TEPA-Cu2(OH)PO4 has good adsorption for CO2 and is an efficient green adsorption material.