We have prepared two new spin-crossover (SCO) Fe(II) complexes, [Fe(II)(ODT)(3)](p-tol)(2)(I) and [Fe(II)(HET)(3)](p-tol)(2)(II). And they were blended with a liquid crystalline (LC) poly(oxetane) (POx). Thermal and spin crossover behavior of the composites then were studied by using a superconducting quantum interference device (SQUID), differential scanning calorimetry (DSC) and extended X-ray absorption fine structure (EXAFS) spectroscopy. When composites carried higher than 20 wt.% of the Fe(II) complexes, they revealed a reversible spin crossover for the low spin (LS) <-> high spin (HS) transition in addition to the thermal transitions, i.e., glass transition and isotropization, of the LC polymer matrix.