An object of the present invention is to provide a method of manufacturing phosphorus pentafluoride and hexafluorophosphate, that can suppress the manufacturing cost and also can manufacture high-quality phosphorus pentafluoride from an inexpensive and low-quality raw material. The present invention relates to a method of manufacturing phosphorus pentafluoride, wherein a raw material which comprises at least phosphorus atoms and fluorine atoms is brought into contact with a carrier gas, thereby a phosphorus pentafluoride is extracted and separated into the carrier gas. The present invention relates to a method of manufacturing hexafluorophosphate, comprising the step of: reacting fluoride with phosphorus pentafluoride obtained by the method of manufacturing phosphorus pentafluoride according to the following chemical reaction scheme, €ƒ€ƒ€ƒ€ƒ€ƒ€ƒ€ƒ€ƒsPF 5 + AF s †’ A(PF 6 ) s wherein s is in the range of 1 ‰¤ s ‰¤ 3, and A is at least one member selected from the group consisting of Li, Na, K, Rb, Cs, NH 4 , Ag, Mg, Ca, Ba, Zn, Cu, Pb, Al and Fe.