By utilizing a flexible tetrapyridinate ligand, tetrakis(4-pyridyloxymethylene) methane(L), a novel multifunctional soft porous framework, [Co(NCS)2(L)]·2H2O·CH3OH (1), was constructed. This framework exhibits quick and selective solvatochromic and vapochromic behavior during a reversible crystal-to-amorphous-to-crystal (CAC) transformation. Importantly, the rapid CAC transition can selectively be triggered by methanol molecules, even at low concentrations of liquid or gaseous methanol. This reproducible transition can be monitored by single-crystal and power X-ray analysis, IR, and UV-vis, which all powerfully illustrate the selectivity and sensitivity of this system. In addition, the typical magnetic behavior of single ion magnets (SIMs) has been successfully introduced into this 3D framework, and the modified dynamic relaxations have been investigated via experimental and theoretical analysis. The consistent observations of both experimental and theoretical results support that the distortions of the metal coordination environments should be responsible for the finely tuned SIM behavior.