Two europium(III) coordination polymers (CPs), namely, poly[[diaquabis(μ-1H-benzimidazole-5,6-dicarboxylato-κN:O,O:O,O:O)(μ-oxalato-κO,O:O,O)dieuropium(III)] dihydrate], {[Eu(CHNO)(CO)(HO)]·2HO} (1), and poly[(μ-1H-benzimidazol-3-ium-5,6-dicarboxylato-κO:O,O:O,O)(μ-sulfato-κO:O':O'')europium(III)], [Eu(CHNO)(SO)] (2), have been synthesized via the hydrothermal method and structurally characterized. CP 1 shows a three-dimensional network, in which the oxalate ligand acts as a pillar, while CP 2 has a two-dimensional network based on a europium(III)-sulfate skeleton, further extended into a three-dimensional framework by hydrogen-bonding interactions. The structural diversity in the two compounds can be attributed to the different acidification abilities and geometries of the anionic ligands. The luminescence properties of 1 display the characteristic europium red emission with CIE chromaticity coordinates (2/3, 0.34). Interestingly, CP 2 shows the characteristic red emission with CIE chromaticity coordinates (0.60, 0.34) when excited at 280 nm and a near-white emission with CIE chromaticity coordinates (0.38, 0.29) when excited at 340 nm.