This review compiles important aspects of the chemistry of polyvalent perfluoroorganohalogen(III and V) compounds of the last three decades and reports on distinctions which are worth mentioning in comparison with non-fluorinated polyvalent organohalogen(III and V) analogues. Besides general synthetic paths to neutral (R F HalX 2 , (R F ) 2 IX, (R F ) 3 I, and R F HalX 4 ), cationic ([R F (R′)Hal]Y and [R F (R′)HalF 2 ]Y), and anionic (M[R F HalX 3 ] and M[(R F ) 2 HalX 2 ]) derivatives of iodine and bromine, transformations at the halogen centre of those polyvalent compounds and selected applications and their use as reagents are referred. Trends of 19 F and 13 C NMR spectroscopic properties of prototypes of polyvalent perfluoroorgano-iodine and -bromine compounds are compiled and interpreted. Structural features of characteristic perfluoroalkyl-, pentafluorophenyliodine(III and V), and few -bromine(III) compounds are presented and compared.