Allylic alkylations are valuable in the construction of versatile carbon-carbon bonds, which are mostly catalyzed by noble transition metals with additional waste byproduct generation. Here, we present the first organophosphine-catalyzed allylic alkylation of (hetero)aryl alkynes with various carbo-nucleophiles. The methodology is highly atom economical and compatible with a wide substrate scope (more than 38 examples). Moreover, the reaction could be easily scaled up, and deuterium labeling experiments have been conducted to elucidate the plausible mechanism. Finally, the protocol has been utilized to achieve the concise total synthesis of natural product (±)-esermethole.