AbstractZirconium diethylene triamine pentamethylene phosphonate and titanium diethylene triamine pentamethylene phosphonate, novel hybrid cation exchange materials of the class of tetravalent metal acid salts, synthesized by sol-gel method has been characterized by spectroscopy and thermal analysis. Distribution coefficient and breakthrough capacity for La3+, Ce3+, Pr3+, Nd3+, Sm3+ (lanthanides) and Th4+, (actinides) have been studied. Based on the differential affinity/selectivity and elution behavior of various metal ions, a few binary and ternary metal ion separations have been carried out.