The understanding of the correlation between the spin-state behaviour and the structural features in transition-metal complexes is of pronounced importance to the design of spin crossover compounds with high performance. However, the study of the influence of ligand symmetry on the spin crossover properties is still limited due to the shortage of suitable structural systems. Herein we report the magneto-structural correlations of three mononuclear Fe(ii) isomers with respect to their ligand symmetry. In this work, two phenyl-substituted meso and optically pure pybox ligands were employed to construct meso (1), optically pure (2), and racemic (3) ligand types of [Fe(pybox)2]2+ complexes. Their magnetic susceptibilities were measured via temperature-dependent paramagnetic 1H NMR spectroscopy. We fitted the midpoint temperatures of the transition (T1/2) of 260 K for 1(ClO4), 247 K for 2(ClO4), and 281 K for 3(ClO4). The influence of structural symmetry on spin crossover was rationalized through density functional theory calculations. The optimized structures of [Fe(pybox)2]2+ complex cations show that the geometric distortion of the central FeN6 coordination sphere is mainly caused by the steric congestions between adjacent phenyl substituents. In these compounds, there is a distinct correlation that more steric congestions produce larger coordination distortion and favor the electron configuration in the high-spin state, which reflects in the increase of T1/2. Additionally, the influence of the counter anion and lattice solvent on the meso series compounds was inspected. It is revealed that multiple factors dominate the spin-state behaviour in the solid state. This work provides deep insight into the effect of ligand symmetry on the spin transition behaviour in spin crossover compounds. It demonstrates that molecular symmetry should be considered in the design of spin crossover compounds.