Alkane σ‐complexes have evolved from a curious phenomenon to an intermediate of intense interest, fuelling research into the area. Over the last fifteen years, metal alkane complex characterisation has evolved to incorporate reports employing UV/Vis, IR and NMR spectroscopy, and X‐ray and neutron diffractometry. Previously, due to the sparse geometric characterisation of alkane σ‐complexes, assumptions regarding bonding geometries and selectivities were made by comparison to related σ‐complexes, or by analysis of CH activation products. This minireview assembles relevant literature that illuminates the metrics of alkane–metal bonding, and critically analyses the binding mode, selectivity and stability of alkane complexes.