AbstractWe reported new in‐situ ternary nano/microcomposite layered double hydroxides/Ag2O/bayerite in trimetallic NiAg/Al layered double hydroxides (LDH) via hydrothermal technique; and characterization by powder X‐ray diffraction (XRD), Fourier transforms infrared spectroscopy (FT‐IR), field emission scanning electron microscopy (FE‐SEM), energy dispersive spectroscopy (EDS), and N2 adsorption‐desorption. The formation of bayerite and silver oxide species on the LDH nanosheet depended on the excess of Al3+ and Ag+ in the solution under alkaline and hydrothermal conditions. The nitrogen isotherm adsorption profile for all ternary composites exhibited uniformity with mesoporous and lamellar characteristics. The surface area of all the composites ranged from 81.17 to 150.23 m2. g−1, the Barret‐Joyner‐Halenda (BJH) pore volume from 0.22 to 0.27 cm3. g−1, and the average pore diameter ranged from 3.47 to 5.78 nm. All composites show a laminar plate‐like structure covered with elongated pieces. The particle size of the composites ranged from 54.86 to 115.96 nm, indicating the size changed from nano to microcomposite because of the different molar ratios of Ag and Ni in the solid. The ternary composite reveals CO2 capture activity with adsorption capacity ranging from 13.93 to 19.61 mmol g−1. © 2024 Society of Chemical Industry and John Wiley & Sons, Ltd.