Coordination polymers can be attractive ion exchange materials because of their crystallinity and semi-flexibility, which are rather opposing properties, and play integral and synergistic roles in introducing unique ion-exchange behavior. In this paper, Ln(3+)/Ce(3+) exchange (Ln(3+) = Nd(3+), Gd(3+), Dy(3+), or Lu(3+)) in a coordination polymer, [Ce(dehp)3], based on di(2-ethylhexyl)phosphoric acid (Hdehp) is studied by distribution coefficient measurements, ion-exchange isotherms, Kielland plot analysis, and morphology observation. The ion-exchange selectivity is in the order Nd(3+) < Gd(3+) < Dy(3+) < Lu(3+) when a small amount of Ln(3+) is loaded, but Lu(3+) ≈ Nd(3+) < Gd(3+) ≈ Dy(3+) for a high loading ratio. The Kielland plot suggests that a steric effect is involved in the reactions, which becomes stronger in the order of Nd(3+)/Ce(3+) < Gd(3+)/Ce(3+) < Dy(3+)/Ce(3+) < Lu(3+)/Ce(3+) for exchange systems. This trend is attributable to the differences in the ionic sizes between an incoming Ln(3+) and original Ce(3+). Scanning electron microscopy observations reveal the generation of a new phase via the Ln(3+)/Ce(3+) exchange. Such a phenomena results from solid-solid transformation, rather than dissolution-recrystallization. The small steric strain in the Nd(3+)/Ce(3+) system leads to the formation of a Nd(3+)-and-Ce(3+) solid-solution, whereas the morphological change is possibly restrained by the strong strain caused by loaded Ln(3+) with an ionic size significantly smaller than the original Ce(3+).