Crystalline [FeL2][BF4]2⋅Me2CO (L=N‐[2,6‐di{pyrazol‐1‐yl}pyrid‐4‐yl]acetamide) is high‐spin at room temperature, and undergoes an abrupt, hysteretic spin‐crossover at T
=137 K (ΔT
=14 K) that proceeds to about 50 % completeness. This is associated with a crystallographic phase transition, from phase 1 (P21/c, Z=4) to phase 2 (P21, Z=48). The cations associate into chains in the crystal through weak intermolecular π⋅⋅⋅π interactions. Phase 2 contains a mixture of high‐spin and low‐spin molecules, which are grouped into triads along these chains. The perchlorate salt [FeL2][ClO4]2⋅Me2CO also adopts phase 1 at room temperature but undergoes a different phase transition near 135 K to phase 3 (P21/c, Z=8) without a change in spin state.