Abstract The anionic products from the reactions between metal(M=Ag,Au,Pd,Pt,Pb and Bi)vapour produced by laser ablation and hexafluorobenzene seeded in carrier gas(Ar1 were studied by means of a homemade reflectron time-of-flight mass spectrometry(RTOF-MS).Experimental results show that the dominant products were【M C6F6]一 complexes for the reactions of Ag,Au,Pd and Pt with C6F6,while the dominant products were【M C6F5]一complexes f0r the reactions of Pb an d Bi with C6F6.The formation mechanisms of the products,including the adsorption of metal cluster anions on hexafluorobenzene and the C— F cleavage induced by metal cluster anions.were discussed.