X‐ray structural analyses revealed the inclusion of biphenyl into the assembled complexes and the composition was confirmed as Fe2(NCS)4(bpy)4(biphenyl)5, Fe(NCS)2(bpa)2(biphenyl)2, and Fe(NCSe)2(bpa)2biphenyl. 57Fe Mössbauer spectroscopy revealed that the spin state remained high spin but the QS value changed by introducing biphenyl molecule in the assembled complex.