A series of previously unknown asymmetrical fluorinated bis(aryl)bromonium, alkenyl(aryl)bromonium, and alkynyl(aryl)bromonium salts was prepared by reactions of C 6 F 5 BrF 2 or 4-CF 3 C 6 H 4 BrF 2 with aryl group transfer reagents Ar′SiF 3 (Ar′=C 6 F 5 , 4-FC 6 H 4 , C 6 H 5 ) or perfluoroorganyl group transfer reagents R F ′BF 2 (R F =C 6 F 5 , trans-CF 3 CFCF, C 3 F 7 C≡C) preferentially in weakly coordinating solvents (CCl 3 F, CCl 2 FCClF 2 , CH 2 Cl 2 , CF 3 CH 2 CHF 2 (PFP), CF 3 CH 2 CF 2 CH 3 (PFB)). The presence of the base MeCN and the influence of the adducts R F ′BF 2 ·NCMe (R F =C 6 F 5 , CF 3 C≡C) on reactions aside to bromonium salt formation are discussed. Reactions of C 6 F 5 BrF 2 with Alk F ′BF 2 in PFP gave mainly C 6 F 5 Br and Alk F ′F (Alk F ′=C 6 F 13 , C 6 F 13 CH 2 CH 2 ), presumably, deriving from the unstable salts [C 6 F 5 (Alk F ′)Br]Y (Y=[Alk F ′BF 3 ] − ). Prototypical reactivities of selected bromonium salts were investigated with the nucleophile I – and the electrophile H + . [4-CF 3 C 6 H 4 (C 6 F 5 )Br][BF 4 ] showed the conversion into 4-CF 3 C 6 H 4 Br and C 6 F 5 I when reacted with [Bu 4 N]I in MeCN. Perfluoroalkynylbromonium salts [C n F 2n+1 C≡C(R F )Br][BF 4 ] slowly added HF when dissolved in aHF and formed [Z–C n F 2n+1 CFCH(R F )Br][BF 4 ].