Using nitrogen rich 2,6-bibenzimidazole-4-hydroxypyridine reacted with 1,6-dibromohexane and 1,8-dibromo-octane the double-ended tridentate ligand 1,6-bis-(2,6-bis(benzimidazolyl)pyridyloxy)hexane and 1,8-bis-(2,6-bis(benzimidazolyl)pyridyloxy)octane were synthesized. Temperature and chemical stimuli-responsive La(Ⅲ) polymer gel with distinct luminescence could be obtained through the ligand and metal ions self-assembly. MR spectra indicate successful synthesized the monomer and the ligand, the TG and XRD were applied to test the performance of polymer. Experiments showed that the polymer gels have reversible temperature stimuli-responsive, and chemical stimuli-responsive when added formic acid. Optical performance reach showed, under UV irradiation, the polymer gels have a distinct luminescence, and maximum emission peaks are located at 419 nm.