By using a new resorcin[4]arene-based tetracarboxylate, three functional coordination polymers (CPs)namely, [(CH3)(2)NH2][Cd2NaL(HCOO)(2)(HCOOH)(H2O)].H2O (1), [(CH3)(2)NH2](2)[CdL].CH3OH.4H2O (2), and [(CH3)(2)NH2][Zn2Na3L2(H2O)(2)].H2O (3)-have been synthesized under solvothermal conditions (H4L = 2,8,14,20-tetra-pentyl-4,10,16,22-tetrakis((4-carboxybenzyl)oxy)-6,12,18,24-tetra-methoxy-resorcin[4]arene and DMF = N,N'-dimethylformamide). The structures of 1-3 have been confirmed by single-crystal X-ray diffraction analyses and further physically characterized. In 1, L and HCOO link Cd(II) and Na(I) ions to yield an unusual three-dimensional (3D) 4-connected heterometallic framework with (4(2).6(4))(4.8(3).10.12) topology. In 2, L anions link Cd(II) ions to give a 3D binodal 4-connected framework with (4(2).6(3).8)(2) topology. In 3, adjacent dodecanuclear heterometallic clusters are joined together by L anions, yielding a two-dimensional (2D) (3,8)-connected (3.4(2))(3(4).4(6).5(6).6(8).7(3).8) network. Most strikingly, CPs 1 and 2 display unusual metal-ion exchange characters. CP 2 shows remarkable reversible adsoption of I-2 molecules. In addition, CPs 1-3 can selectively adsorb organic dyes and exhibit highly luminescent sensing properties for small molecules.