The first example of a copper(I)-catalyzed intramolecular aminotrifluoromethylation of unactivated alkenes using (TMS)CF3 (trimethyl(trifluoromethyl)silane) as the CF3 source is described. A broad range of electronically and structurally varied substrates undergo convenient and step-economical transformations for the concurrent construction of a five- or six-membered ring and a C-CF3 bond toward different types of trifluoromethyl azaheterocycles. The methodology not only circumvents use of expensive electrophilic CF3 reagents or the photoredox strategy but also expands the scope to substrates that are difficult to access by the existing methods. Mechanistic studies are conducted, and a plausible mechanism is proposed.