The adsorption mechanism of Al(III) and Fe(III) ions on bastnaesite surfaces was investigated by a combination of DFT calculation, XPS analysis, adsorption isotherm study and adsorption kinetic investigations. DFT calculation results indicated that 〖≡CeOH〗^0 and ≡〖CO_3 H〗^0 are primary functional groups on bastnaesite surfaces. XPS analysis reveals that Al(III) and Fe(III) ions adsorbed onto the bastnaesite surfaces through the interaction between aluminium/iron hydroxide species and oxygen atoms of surface 〖≡CeOH〗^0 groups. No interaction between aluminium/iron hydroxide species and ≡〖CO_3 H〗^0 groups was detected. Adsorption isotherm studies demonstrated that the adsorption data of Al(III) and Fe(III) ions is fitted relatively well by Freundlich equations, the adsorption kinetic characteristics fitted to pseudo-second order model. Freundlich constants suggested favorable process for Al(III) and Fe(III) ions adsorption, and each adsorbed metal hydroxide specie complex with at least two oxygen atoms of surface 〖≡CeOH〗^0 groups.