The enhanced reactivity of [WF5]+ over WF6 has been exploited to access a neutral derivative of elusive WF5. The reaction of WF6(NC5H5)2 with [(CH3)3Si(NC5H5)][O3SCF3] in CH2Cl2 results in quantitative formation of trigonal‐dodecahedral [WF5(NC5H5)3]+, which has been characterised as its [O3SCF3]− salt by Raman spectroscopy in the solid state and variable‐temperature NMR spectroscopy in solution. The salt is susceptible to slow decomposition in solution at ambient temperature via dissociation of a pyridyl ligand, and the resultant [WF5(NC5H5)2]+ is reduced to WF5(NC5H5)2 in the presence of excess C5H5N, as determined by 19F NMR spectroscopy. Pentagonal‐bipyramidal WF5(NC5H5)2 was isolated and characterised by X‐ray crystallography and Raman spectroscopy in the solid state, representing the first unambiguously characterised WF5 adduct, as well as the first heptacoordinate adduct of a transition‐metal pentafluoride. DFT‐B3LYP methods have been used to investigate the reduction of [WF5(NC5H5)2]+ to WF5(NC5H5)2, supporting a two‐electron reduction of WVI to WIV by nucleophilic attack and diprotonation of a pyridyl ligand in the presence of free C5H5N, followed by comproportionation to WV.