Like other metal cyanides, solid potassium ferricyanide has a complicated polymeric structure. The polymer consists of octahedral 3− centers crosslinked with K+ ions that are bound to the CN ligands. The K+---NCFe linkages break when the solid is dissolved in water.
The compound has widespread use in blueprint drawing and in photography (Cyanotype process). Several photographic print toning processes involve the use of potassium ferricyanide. Potassium ferricyanide was used as an oxidizing agent to remove silver from color negatives and positives during processing, a process called bleaching. Because potassium ferricyanide bleaches are environmentally unfriendly, short-lived and capable of releasing cyanide gas if mixed with acid, bleaches using ferric EDTA have been used in color processing since the 1972 introduction of the Kodak C-41 process. In color lithography, potassium ferricyanide is used to reduce the size of color dots without reducing their number, as a kind of manual color correction called dot etching. It is also used in black-and-white photography with sodium thiosulfate (hypo) to reduce the density of a negative or gelatin silver print where the mixture is known as Farmer's reducer; this can help offset problems from overexposure of the negative, or brighten the highlights in the print.
Potassium ferricyanide is also one of two compounds present in ferroxyl indicator solution (along with phenolphthalein) which turns blue (Prussian blue) in the presence of Fe2+ ions, and which can therefore be used to detect metal oxidation that will lead to rust. It is possible to calculate the number of moles of Fe2+ ions by using a colorimeter, because of the very intense color of Prussian blue Fe43.