The first transition metal‐free, site‐specific umpolung trifluoromethylthiolation of tertiary alkyl ethers has been developed, achieving the challenging tertiary C(sp3)‐SCF3 coupling under redox‐neutral conditions. The synergism of organophotocatalyst 4CzIPN and BINOL‐based phosphorothiols offers a promising polarity‐reversal catalytic combination. This can site‐selectively cleave tertiary sp3 C‐O ether bonds in complex molecules initiated by a polarity‐matching hydrogen atom transfer (HAT) event. The incorporation of several competing benzylic and methine C(sp3)‐H bonds in alkyl ethers has little influence on the regioselectivity. Selective difluoromethylthiolation of C‐O bonds has also been achieved. This represents not only an important step forward in trifluoromethylthiolation but also a promising means for site‐selec‐ tive C‐O bond functionalization of unsymmetrical tertiary alkyl ethers.