A conceptually novel strategy with achiral pyridine as the ancillary ligand to stabilize high‐valent copper species for the first asymmetric radical oxytrifluoromethylation of alkenes with alcohols under CuI/phosphoric acid dual‐catalysis has been developed. The transformation features mild reaction conditions, a remarkably broad substrate scope and excellent functional group tolerance, offering an efficient approach to a wide range of trifluoromethyl‐substituted tetrahydrofurans bearing an α‐tertiary stereocenter with excellent enantioselectivity. Mechanistic studies support the presumed role of the achiral pyridine as a coordinative ligand on copper metal to stabilize the key transient reaction species involved in the asymmetric induction process. Magic pyridine: Achiral pyridine has been shown to be crucial for accomplishing the first asymmetric radical oxytrifluoromethylation of unactivated alkenes with alcohols. The remarkably enhanced enantioselectivity observed has been accounted for by a stabilizing effect of pyridine on high‐valent copper intermediates as an ancillary ligand.