Three three-dimensional Hofmann-type metal-organic frameworks (MOFs) [Fe(bpn){Ag(CN) 2} 2]·Ph 2S ( 1·Ph 2 S, bpn = 1,4-di(pyridin-4-yl)naphthalene, Ph 2S = diphenylsulfide), [Fe(bpn){Ag(CN) 2} 2]·Ph 2SO ( 1·Ph 2 SO, Ph 2SO = diphenylsulfoxide) and [Fe(bpn){Ag(CN) 2} 2]·Ph 2SO 2 ( 1·Ph 2 SO 2, Ph 2SO 2 = diphenylsulfone) were synthesized by employing sulfur-containing aromatic guests varying in oxidation states. 1·Ph 2 S performed a complete four-step spin crossover (SCO) behavior with the sequence of HS↔LS 1/3HS 2/3↔LS 1/2HS 1/2↔LS 2/3HS 1/3↔LS, while an incomplete two-step SCO profile with the sequence of HS↔LS 1/3HS 2/3↔LS 2/3HS 1/3 and a faint SCO behavior at low temperature for 1·Ph 2 SO and 1·Ph 2 SO₂. Photomagnetic experiments indicate the light-induced excited spin-state trapping (LIESST) effect in 1·Ph 2 S and the bi-directional LIESST effect for 1·Ph 2 SO and 1·Ph 2 SO₂. Variable-temperature structural analyses reveal the evolution of host-guest synergy and highlight the mechanism of adaptive deformation of guests mediated by phenyl rotation amid spin transition. As the oxidation state of sulfur-containing guests increases, the host-guest cooperation within the lattice is limited by the steric effect, which stabilizes the high-spin state and consequently diminishes the SCO capability in this system. These results demonstrated herein open a new perspective on host-guest chemistry within SCO frameworks.