AbstractBenzenediols react with 2 equiv of secondary phosphine chalcogenides in the CCl4–Et3N system under mild conditions (50–52°C, 1.5–13 h) to give phosphinochalcogenoic O‐diesters in 62–91% isolated yields. © 2012 Wiley Periodicals, Inc. Heteroatom Chem 23:322–328, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.21020