By slow reaction between colorless (AgW2O2F9)-W-I and elemental F-2 in liquid anhydrous HF, violet platelike single crystals of Ag(WOF5)(2) were grown. The crystal structure of Ag(WOF5)(2) consists of layers built from Ag2+ cations bridged by [WOF5](-) anions and not, as previously assumed, from infinite [Ag-II- F](+)(infinity) chains and [W2O2F9](-) anions. A majority (97%) of the disordered Ag-II cations are found with square-planar coordination of F/O ligands within the same layer, and they form additional long contacts with O/F atoms originating from the neighboring layers. The remaining 3% the of Ag(II) ions are coordinated only by F atoms in a square-planar fashion. The magnetic moments of Ag2+ from the same layer are almost perfectly antiferromagnetically aligned. Weak ferromagnetic interlayer interactions cause a small tilt (similar to 1.5 degrees) of the magnetic moments, resulting in canted antiferromagnetism. Because of the lowering of the symmetry of [WOF5](-) in the solid state, the vibrational spectra show more bands than expected for regular C-4 upsilon, symmetry. The electronic spectrum of Ag(WOF5)(2) is reported and analyzed.