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A family of Group 4 post‐metallocene catalysts, supported by fluorine‐functionalized tridentate ligands with the fluorine substituent in the locality of the metal center, is described. For the first time, the contentious CH⋅⋅⋅FC interaction has been characterized by a neutron diffraction study, which has allowed the position of the hydrogen atoms to be accurately determined. The nature of the weak intramolecular CH⋅⋅⋅FC contacts in these complexes in solution and the solid state was probed by using multinuclear NMR spectroscopy in tandem with neutron and X‐ray crystallography. Evidence is presented to demonstrate that the spectroscopic CH⋅⋅⋅FC coupling occurs “through‐space” rather than “through‐bond” or by M⋅⋅⋅F coordination. The titanium catalysts exhibit excellent activities and high co‐monomer incorporation in olefin polymerization. The observed intramolecular CH⋅⋅⋅FC …