This study aims to develop an inexpensive, environmentally-friendly adsorbent for capturing CO2 using coconut shells, widely abundant in Asian agricultural waste. The raw coconut shell adsorbent (CS) has undergone dual functionalization utilizing Chlorella microalgae and magnesium oxide (MgO) to enhance its physicochemical properties. Through dual functionalization, minimizing the loss of surface area and reducing the temperature sensitivity often occurring during CO2 adsorption is possible. The surface morphology, functional groups, and thermochemical properties of CS-hydrochar were characterized and evaluated. The characterization demonstrates the successful development of the ternary composite (HCS-A-Mg), with a specific surface area of 1045 m2/g and containing nitrogen and metal oxide functional groups. XRD analysis of HCS-A-Mg reveals crystalline peaks at 36.8°, 42.9°, and 63°, confirming the successful impregnation of MgO. The adsorption result showed that HCS-A-Mg exhibits a higher CO2 adsorption capacity of 2.63 mmol/g, 50% higher than pristine hydrochar (HCS). The adsorption study revealed that the CO2 adsorption capacity of HCS-A-Mg can be maximized to 3.23 mmol/g at 101 °C and 4.6 bar. Adsorption isotherms shows that the non-linear Sips model best describes the adsorption process, indicating a multilayer adsorption mechanism with profound surface heterogeneity of n = 2.3 for HCS-A-Mg, signifying higher accessibility of gas molecules deep into pores, enabling a variety of adsorption sites for CO2 binding. Selectivity and reusability studies were conducted to validate the adsorbent applicability for industrial applications. HCS-A-Mg has higher CO2/N2 selectivity by 41–57% and 0.05% loss of adsorption capacity after the 10th cyclic operation, suggesting their suitability for industrial applications. This finding underscores the potential of microalgae and magnesium oxide in advancing carbon capture technology and addressing environmental challenges.