The noncovalent interactions and remote ligand effects in catalysis have attracted a large attention in the last years. The rationalization of such interactions is tricky and often their role can be elucidated only with a detailed mechanistic study. Here we report the case of fluorinated ligand systems showing a very peculiar behavior in the catalysis of olefin polymerization. The results reported aim to clarify the origin of such behavior underlying the nature of the control of the fluorinated groups on the key steps of the polymerization. These insights can offer new cues to rationalize similar evidences in other reaction fields.