Taking advantages of both azide and cyanide bridges in magnetism and synthesis, an azido-cyanide mixed-bridged octanuclear [(Fe4Ni4II)-Ni-III] SMM of [{(enbzpy)Ni-2(mu(1,1)-N-3)(2)center dot(DMF)}{Tp*Fe(CN)(3)}(2)](2)center dot 2DMF center dot 14H(2)O (1) was explored and characterized, which exhibits slow relaxation of the magnetization and an S = 6 ground state benefit from the end-on azido bridges.