Taking advantages of both azide and cyanide bridges in magnetism and synthesis, an azido-cyanide mixed-bridged octanuclear [FeIII4NiII4] SMM of [{(enbzpy)Ni2(μ1,1-N3)2·(DMF)}{Tp*Fe(CN)3}2]2·2DMF·14H2O (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.