A mixed ligand approach was exploited to synthesize a new series of MnII -based coordination polymers (CPs), namely, CP1 {[Mn(μ-dpa)(μ-4,4'-bp)]⋅MeOH}∞ , CP2 {[Mn3 (μ-dpa)3 (2,2'-bp)2 ]}∞ , CP3 {[Mn3 (μ-dpa)3 (1,10-phen)2 ]⋅2 H2 O}∞ , CP4 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅H2 O}∞ , CP5 {[Mn2 (μ-dpa)2 (μ-4,4'-bpe)2 ]⋅1/2 DEF}∞ , and CP6 {[Mn(μ-dpa)(μ-4,4'-bpe)1.5 ]⋅1/2 DMA}∞ (dpa=3,5-dicarboxyphenyl azide, 2,2'-bp=2,2'-bipyridine, 1,10-phen=1,10-phenanthroline, 4,4'-bpe=1,2-bis(4-pyridyl)ethylene, 4,4'-bp=4,4'-bipyridine, DEF=N,N-diethylformamide, DMA=N,N-dimethylacetamide), to develop multifunctional CPs. Various techniques, such as single-crystal X-ray diffraction (SXRD), FTIR spectroscopy, elemental analysis, and thermogravimetric analysis, were employed to fully characterize these CPs. The majority of the CPs displayed a four-connected sql topology, whereas CP4 and CP6 exhibited a two-dimensional SnS network architecture, which was further entangled in a polycatenation mode. Compound CP1 displayed an open framework structure. The CPs were scaled down to the nanoregime in a ball mill for cell imaging studies. Whereas CP2 and CP4 were employed for cell imaging with RAW264.7 cells, CP1 was exploited for both cell imaging and heterogeneous catalysis in a cyanosilylation reaction.