Chiral 1D coordination compounds formed by association of either of the enantiomers of [ML(MeOH)Cl]Cl (with M=Mn II or Fe II ; L stands for either R or S enantiomer of a pentadentate macrocycle) and NBu 4 [Fe III (bpb)(CN) 2 ], namely: 1D‐[{Fe III (bpb)(CN) 2 }{M II (L R )}](PF 6 ) and 1D‐[{Fe III (bpb)(CN) 2 }{M II (L S )}](PF 6 ) with M=Mn ( 2R , 2S ) and Fe ( 3R , 3S ). The bis(triphenylphosphine)iminium salt of the metallo‐ligand, PNP[Fe III (bpb)(CN) 2 ]⋅2H 2 O, 1 b , is also described. Their preparations, crystal structures, optical and magnetic properties are reported. Mössbauer spectroscopy confirmed the oxidation state in the [Fe II −Fe III ] chain, for which AC susceptibility suggests SCM behavior, but for very low T .