We present a novel approach for in situ generation of acyloxyphosphoniums by premixing iodobenzene dicarboxylates and triphenylphosphine, resulting in efficient thioester synthesis (up to 100% yield). Stable solid iodobenzene dicarboxylates, achieved via carboxylate exchange, serve as hypervalent iodine precursors. The resulting acyloxyphosphoniums allow convenient one-pot thioester synthesis under mild conditions. Our method demonstrates facile acyloxyphosphonium production from iodobenzene dicarboxylates and Ph₃P, enabling diverse thioester preparation. ESI-MS analysis confirms acyloxyphosphonium ion formation, pivotal in acylation. This strategy holds potential for combinatorial thioester synthesis and broader nucleophile modification applications.