In our efforts to investigate the influence of alkali-metal ions on the formation of metal complexes with polyhalogen-substituted benzenedicarboxylates, two manganese(II) complexes of tetrachlorophthalic acid (1,2-H2BDC-Cl4), [Mn2(1,2-BDC-Cl4)2(H2O)9]·H2O (1) and [MnK2(1,2-BDC-Cl4)2(H2O)4]n (2), were synthesized and structurally characterized. Single-crystal X-ray diffraction studies have revealed that complexes 1 and 2 crystallize in space groups P1̅ and Pbcn, respectively. Complex 1 shows a discrete dinuclear structure, while complex 2 features a two-dimensional heterometallic framework containing rare Mn–O–K linkages. The results clearly suggest that the introduction of alkali metal ions does play a critical role in the construction of complexes 1 and 2 with distinct dimensionality and connectivity. Their spectroscopic, thermal, and fluorescence properties have also been studied briefly.