The directed assembly of N,N‐bis(benzimidazol‐2‐yl‐methyl)amine (BMA), 4,4′‐bipyridine (4,4′‐bipy) and NiII or MnII salts resulted in the formation of  the novel compounds [{Ni(BMA)(SCN)2}2]·(μ‐4,4′‐bipy)(DMSO)2 (1) and [{Mn(BMA)(SCN)2}2]·(μ‐4,4′‐bipy) (2), which were characterized by single‐crystal X‐ray diffraction, elemental analysis, IR spectroscopy, UV/Vis spectroscopy and magnetic measurement. The X‐ray single‐crystal analysis reveals that 1 and 2 are discrete dinuclear compounds bridged by 4,4′‐bipy, further arranged in multidimensional supramolecular networks which are stabilized by different modes of hydrogen bonding and π–π interactions. Variable‐temperature magnetic measurements (2–300 K) of 1 and 2 were modeled with magnetic coupling constants J = –0.16 and –0.022 cm–1, respectively showing the weak antiferromagnetic coupling between the two metal ions in each dinuclear complex, which is also observed for similar 4,4′‐bipyridine bridging complexes.