Linkage isomers involving changes in the bonding mode of ambidentate ligands have potential applications in data storage, molecular machines, and motors. However, the observation of the cyanide-linkage-isomerism-induced spin change (CLIISC) effect characterized by single-crystal X-ray diffraction remains a considerable challenge. Meanwhile, the high-spin and low-spin states can be reversibly switched in spin-crossover (SCO) compounds, which provide the potential for applications to data storage, switches, and sensors. Here, a new perovskite-type SCO framework (PPN)[Fe{Ag(CN)2}3] (PPN+ = bis(trisphenylphosphine)iminium cation) is synthesized, which displays the unprecedented aging and temperature dependences of hysteretic multistep SCO behaviors near room temperature. Moreover, the thermal-induced cyanide linkage isomerization from FeII-N≡C-AgI to FeII-C≡N-AgI is revealed by single-crystal X-ray diffraction, Raman, and Mössbauer spectra, which is associated with a transition from the mixed spin state to the low-spin state and a dramatic volume shrinkage. Considering the wide use of cyanogen in magnetic systems, the association of CLIISC and SCO opens a new dimension to modulate the spin state and realize a colossal negative thermal expansion.