(Dibenzoylmethanato)boron difluoride (DBMBF2) was found to form with benzene (B) and its methylated derivatives (MB) in cyclohexane (cHex) two types of ground state complexes. The first complexes with low stoichiometries 2 : 1, 1 : 1 and 1 : 2 do not fluoresce when they are excited. On the other hand, the ground state complexes with high stoichiometry, DBMBF2-(B)(n) or DBMBF2-(MB)(n) (with n>> 2), exhibit a strong fluorescence in their excited states. These findings differ from the previous results, where the strongly fluorescing complexes have been argued to be the 1 : 1 and 1 : 2 exciplexes, complexes of the singlet excited state of DBMBF2 with one or two B or MB molecules. These differences are discussed in terms of the solute-solute and solute-solvent interactions when DBMBF2 and MB are solutes in cyclohexane or when MB is a co-solvent of cyclohexane in binary mixtures of DBMBF2. We also argue that the use of well-suited analytical methods is important for the determination of the nature of the various complexes. Furthermore, to understand the nature of the interactions between benzene and DBMBF2 molecules, we attempt to predict the sites of interaction between DBMBF2 and benzene molecules by determining theoretically the structure of the 1 : 1 complex.