Reaction of Mn(II) salts with a meridional tricyanido iron(III) linker, [Fe(bbp)(CN)3]2− (H2bbp=bis(2‐benzimidazolyl)pyridine) was investigated in presence of two different N‐donor blocking ligands. Two heterometallic Mn(II)/Fe(III) aggregates viz. [Mn(cptp)2][Fe(bbp)(CN)3] ⋅ 3H2O (1) (cptp=4’‐(4‐chlorophenyl)‐2,2’ : 6’,2’’‐terpyridine) and [Mn(CH3OH)2(μ‐NC)3Fe(bbp)]n (2) are isolated and characterized by using analytical, spectroscopic, structural, electrochemical and magnetic investigations. Single crystal X‐ray diffraction analysis show that compound 1 is a heterobimetallic complex salt, while compound 2 is a cyanido bridged Mn(II)−Fe(III) ladder shaped chain. The electrochemical behaviours of both compounds 1 and 2 exhibit multiple redox accessible states associated with the corresponding metal centres. Investigation of magnetic properties of 2 manifest interplay of antiferromagnetic interaction between low‐spin Fe(III) and high‐spin Mn(II) ions.