The structural, electronic and magnetic properties of Fe/Li(Ag, Li-Ag)Br/Fe (001) tunnel junctions are investigated by means of a first principles Green’s function technique for surface and interfaces implemented within tight-binding linear muffin-tin orbital (TB-LMTO) method, and in conjunction with the coherent potential approximation (CPA). The spin dependent transport properties, in current-perpendicular-to-plane (CPP) geometry, are studied by means of Kubo-Landauer approach implemented within TB-LMTO-CPA formalism and including vertex corrections. Total energy calculations evidenced that Fe/Li(Ag)Br (001) interfaces with Fe atoms located above Li(Ag) and Br sites are energetically most stable ones. Metal induced gap states (MIGS) localized on both anionic and cationic sites are observed in LiBr and AgBr barriers. The interfacial iron’s magnetic moments (≈3 μB) are enhanced over the corresponding bulk value due to low coordination number at Fe/Li(Ag)Br interfaces. A small ferromagnetic (FM) exchange coupling, that exponentially decrease with the barrier thickness, is evidenced in case of Fe/LiBr/Fe (001) heterostructures. An oscillatory exchange coupling between ferro- and antiferromagnetic (AFM) states with decreasing amplitude is obtained in case of Fe/AgBr/Fe (001) multilayer structures. Spin dependent transport properties of Fe/LiBr/Fe MTJs are determined by the interface resonate states (IRS) at Fe/LiBr (001) interfaces and characterized by very high TMR values (≈35000 %) as for of NaCl based junctions. In case of Fe/AgBr/Fe (001) tunnel junction the transport properties are determined by the complex band structure of AgBr barrier and TMR values as high as 4000 % are predicted. Electronic and magnetic properties of Fe/Li(Ag)Br (001) interfaces and spin dependent transport properties of Fe/Li(Ag)Br/Fe (001) junctions are found to be very sensitive on the interface geometry.