ContentsI. Introduction 935 II. The influence of fluorine-containing substituents on the properties of the P(III) atom. Photoelectron 935 spectroscopic and electrochemical data III. Synthesis of fluoroalkoxy-derivatives of P(III) 938 IV. Reactions of fluoroalkyl phosphites 948 V. Conclusion 966 Abstract. The review surveys and gives a systematic account of the electronic structures, syntheses, and chemical properties of fluoroalkyl derivatives of trivalent phosphorus (phosphites, thiophosphites, and amidophophites). The methods of preparation and reactivities of fluoroalkyl phosphites are compared with those of unsubstituted phosphites. The bibliography includes 420 references.