Abstract This paper aims to present the recent results progress on diaminododecylphosphonic acid (DADTMTPA) as an extractant of cerium (III) from Ce(NO 3 ) 3 .6H 2 O solution medium. Different parameters including pH, temperature, extractant concentration, and foreign ions present in the aqueous phase were examined to investigate the extractional mechanism. The optimum conditions of solvent extraction of Ce(III) are as follows: under experimental conditions of 298 K and the initial concentration of Ce(III) being kept at 10 −4 M at pH 3.50. The agitation duration of 5 min for a volume ratio equal to 2, and the best yield is 77 % in one‐step. An increase in the temperature reduced the extraction process. The DADTMTPA extracts Ce(III) after the second cycle with a yield of 95 %. The extraction thermodynamic parameters such as Δ G , Δ H and ΔS are also determined and reported. On the other hand, density functional theory (DFT) based on B97D3 functional with 6‐311++G(d,p) basis set analysis and molecular dynamics simulations were used to extremely fast methods at calculating the non‐bonded interactions and to understand its properties of molecular interactions, which have proved to be an adopted and useful tool to predict and describe the chemical behavior of the evolution of the system.