The chemical bond between a transition metal and a methyl group (M-CH 3 ) is typically defined as a single covalent bond, which is of fundamental significance and general interest in understanding the structural properties and reactivity of transition metal alkyl compounds. Herein, we demonstrate that the M-CH 3 bonding involves varying σ and π components and thus should be best described in terms of the partial double M═CH 3 bond. The often-neglected π bonding stems from an occupied π-symmetric orbital of the methyl group comprising all three C-H σ bonds (but one C-H' contributes more than the other two) and a vacant low-lying metal d(π) orbital, and is associated with the intramolecular C-H'···M agostic effect (i.e., an acute M-C-H' angle and a short H'···M distance), whose origin is still controversial. We quantify the geometric and energetic impacts of the π interaction involved in the M-CH 3 bond by explicitly computing the intramolecular π CH' → d M interaction with the ab initio valence bond (VB) theory. Our computations of the ligand-free [TiCH 3 ] 3+ and a series of metallocene catalysts provide a direct proof for the presence of the π bonding in M-CH 3 bonds, which is the cause for the agostic effect. The partial double M═CH 3 bonding model is not only validated by a range of bonding analyses including VB self-consistent field (VBSCF)-based energy decomposition and quantum theory of atoms in molecules (QTAIM) but also authenticated by the specific activity of double M═CH 3 bonds in the C-H activation and olefin insertion. More importantly, the σ bond gradually switches from a classical covalent bond to a novel charge-shift bond with the π bonding becoming increasingly significant. We anticipate that the recognition of the π interaction between electrophilic metal centers and C-H bonds can benefit the understanding of the nature of metal-carbon bonds in transition metal ethyl, alkyl, and carbene compounds.