This chapter reviews the literature published during 2013 relating to phosphine chalcogenides R3P=X (X = O, S, and Se). New routes developed for the synthesis of phosphine chalcogenides are surveyed. The methods comprise preparations from simple building blocks, such as P-chlorides and secondary phosphine chalcogenides, or modifications of existing molecules. The reactivity of P-chalcogenides was also studied with special emphasis on the deoxygenations that are relevant to the development of in situ catalytic versions of the Wittig, Appel and Mitsunobu reactions. At the end of the chapter new results on the complex formation of phosphine chalcogenides are summarised.