Two azido-bridged homospin Fe(II)/Co(II) coordination polymers [Fe₂(Bzp)₂(N₃)₄]_n (1) and [Co₄(Bzp)₄(N₃)₈·(MeOH)₂]_n (2) (bzp = 2-benzoylpyridine) are prepared, which consist of one-dimensional neutral chains with pure EO-azido (μ₂-1,1-N₃) bridges. Magnetically, both 1 and 2 exhibit considerable intrachain ferromagnetic interactions which benefit from the EO-azido bridging mode, leading to typical single-chain magnet (SCM) behavior under both the “infinite-size” and “finite-size” regime and pronounced hysteresis loops. As far as the bridging network is concerned, complex 1 represents not only a rare example of homospin Fe(II)-based SCMs but also the first Fe(II) chain compound with pure EO-azido bridges.