It can be used as a fluorinating reagent in organic syntheses (fluorination of alcohols, carboxylic acids or carbonyl compounds) and has advantages over sulfur tetrafluoride in that milder conditions can be employed and it is a liquid rather than a gas.

The first reported synthesis of selenium tetrafluoride was by Paul Lebeau in 1907, who treated selenium with fluorine:[1] A synthesis involving more easily handled reagents entails the fluorination of selenium dioxide with sulfur tetrafluoride:[2] An intermediate in this reaction is seleninyl fluoride (SeOF2).

VSEPR theory predicts a pseudo-trigonal pyramidal disposition of the five electron pairs around the selenium atom.

In solution at low concentrations this monomeric structure predominates, but at higher concentrations evidence suggests weak association between SeF4 molecules leading to a distorted octahedral coordination around the selenium atom.

In HF, SeF4 behaves as a weak base, weaker than sulfur tetrafluoride, SF4 (Kb= 2 X 10−2): Ionic adducts containing the SeF3+ cation are formed with SbF5, AsF5, NbF5, TaF5, and BF3.