Bismuth readily forms a variety of tri‐ and pentavalent organic derivatives by the reactions of bismuth halides with Grignard, organolithium, organozinc, or organoaluminum reagents. Bismuth(III) triaryl compounds are readily oxidized by chlorine and bromine to triaryl dihalides, while iodine reacts to produce aryl bismuth iodides. Some organobismuth compounds are Lewis acidic, showing the ready formation of higher coordination number adducts with traditional ligands. A variety of organobismuth compounds with bismuth–bismuth and bismuth–transition metal bonds are described. Organobismuth(V) have found uses as selective oxidants and aryl transfer reagents.