Single-molecule magnets (SMMs) with a large magnetization reversal barrier are predominated by the lanthanide systems due to their strong spin–orbit coupling (SOC). However, the transition metals have also emerged as potential contenders and the largest magnetic anisotropy has been identified for a cobalt system among any d-series-based SMMs (Bunting et al. Science 2018, 362, eaat7319). In this work, we have explored the magnetic anisotropy in highly axial ligand field systems of metallocene, having different d-subshell (3d4, 4d4, and 5d4). The wave function-based multireference methods including static and dynamic electron correlations have been employed to investigate the zero-field splitting (ZFS) parameters. Here, we report exceptionally large magnetic anisotropy for a 5d complex of [WCp2]0 with the highest energy barrier that is nearly twice as high as the previous record value for the Co complex. We have also observed that the axial ZFS parameter (D) is increasing down the group in the order of 3d < 4d < 5d, pertaining to a large SOC.