The structure–property correlation of [Co(terpy)₂]²⁺, which shows a spin crossover at 270 K, has been computationally investigated based on its variable temperature crystal structures. Among the employed DFT functionals, only the re-parametrized hybrid B3LYP* functional could describe the correct spin transition temperature. Explicit consideration of metal–ligand sigma bonding with dynamic electron correlation is found to be necessary for an accurate determination of the SCO temperature with multi-reference calculations. The metal–ligand axial bond distances are found to be the most significant internal coordinates in deciding SCO. A small structural change along the axial distance causes a change in the t_2g orbital splitting pattern and a reorientation of the magnetization axes at the SCO temperature. The complex shows an unusual triaxial magnetic anisotropy, with an easy axis of magnetization developing at higher temperatures. The strong coupling of low-frequency wagging motion of the two terpyridine ligands with the spin states of the complex provides an effective pathway for the relaxation of magnetization, resulting in a small magnetic anisotropy barrier.