As a star ligand, the construction of coordination polymers (CPs) based on tetrakis(4-carboxyphenyl)ethylene (H4TCPE) has drawn much attention, due to not only the various coordination configurations but also the intriguing chromophore feature causing aggregation-induced emission (AIE). Herein, by the solvothermal reaction of H4TCPE as connected nodes with lanthanide La(III) salts, the first example of the La(III)-TCPE-based CP (1) has been obtained. The structural analyses indicate that 1 exhibits a 3D framework connected by the sharing carboxylate groups with two kinds of 1D rhombic channels when viewed along the c direction. The photophysical properties of 1 have been explored by luminescence, photoluminescence decay, and quantum yield in the solid state. 1 shows strong luminescence in tetrahydrofuran that was attributed to a "pseudo-AIE process" and sensitive and selective sensing activity of Fe3+ toward metal ions via the obvious luminescent quenching. The sensing mechanism has been investigated and reveals a synergetic effect of the competitive absorption and weak interactions between 1 and Fe3+. Moreover, the high porosity, multiple conjugated pi-electrons within the tetrakis(4-carboxyphenyl)ethylene backbone, and the uncoordinated carboxyl oxygen sites in this material also provide the capacity for iodine adsorption. The adsorption experiments indicate that 1 could efficiently remove almost complete I-2 from the cyclohexane solution after 24 h contact time with an adsorption capacity of 690 mg/g toward I-2.