Vibrationally resolved electronic spectra of small heteroclusters B nS m of benzene (B) and sulfur hexafluoride (S) have been obtained by resonant two-photon ionization spectroscopy. Some spectroscopic details of the B 1S 1 and B 1S 2 complexes were studied in the spectral regions near the S 0S 1, 0 0 0 and 6 1 0 transitions of the benzene monomer. A nonvanishing 0 0 0 vibrational band has been observed for B 1S 1 with a C 3v equilibrium symmetry. For this cluster we have determined the ionization potential IP=9.180 +-0.005 eV as well as the binding energies of B 1S 1 and B 1S + 1. In view of the geometry of the complexes B 1S m ( m=1−4) we found that until m=3 the SF 6 molecules are localized on one side of the benzene molecular plane, while for B 1S 4 the symmetrical arrangement with two S 2 groups on each side is favoured. The fragmentation of (B n S m ) + clusters is restricted to the loss of S 1 molecules while emission of B 1 molecules has not been observed.