Two novel ReIV compounds of formula (Hbpym)2[ReIVBr6]·4H2O (1) and (H4biim)[ReIVBr6]·4H2O (2) [Hbpym+ = 2,2′-bipyrimidinium cation and H4biim2+ = 2,2′-biimidazolium dication] have been prepared and magnetostructurally characterized. 1 and 2 exhibit distinct crystal packing, and the presence of weak intermolecular contacts, such as Re–Br···Br–Re (1 and 2), Re–Br···(H2O)···Br–Re (1 and 2), and Re–Br···π···Br–Re (2), lead to different magnetic behaviors. While 1 is antiferromagnetic, 2 is a ferromagnetic compound and indeed the first example of ferromagnetic salt based on the hexabromorhenate(IV) anion. These results suggest a straightforward synthetic route to the preparation of new ferromagnetically coupled ReIV compounds.