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A unified strategy for the deoxygenative or desulfurative pyridylation of various alcohols and thiols has been developed through a single‐electron transfer (SET) process of frustrated Lewis pairs (FLPs) derived from pyridinium salts and PtBu3. Mechanistic studies revealed that N‐amidopyridinium salts serve as effective Lewis acids for the formation of FLPs with PtBu3, and the generated phosphine radical cation ionically couples with the in situ generated xanthate, eventually affording the alkyl radical through facile β‐scission under photocatalyst‐free conditions. The reaction efficiency was further accelerated by visible‐light irradiation. This method is conceptually appealing by using encounter complexes in FLP chemistry to promote SET, which provides a previously unrecognized opportunity for the selective heteroarylation of a diverse range of alcohols and thiols with various functional groups, even in complex settings under mild reaction conditions. [ABSTRACT FROM AUTHOR]