Extensive ab initio calculations have been carried out on the benzene-Rh+ (Rh+-C6H6) complex, the Rh+(C6H6)(2) sandwich complex and the Rh-2(+)... benzene interaction products, viz., Rh-2(+)-C6H6 and Rh-2(+)-C6H4. The "physisorbed" benzene-Rh+ was found to be in a (3)A(2) state with C-6 upsilon symmetry. The ground state of the Rh+(C6H6)(2) sandwich complex is (3)A(2) with C-2 upsilon symmetry. Although the optimization of the ground state of the sandwich complex was carried out in C-2 upsilon symmetry, no symmetry breaking distortion in the structure of the benzene moiety was found in the final optimized geometry. The relative strength of binding of benzene with the Rh+ cation in these two complexes has also been compared. The interaction of Rh-2(+) and benzene has been found to favor the formation of two different products consistent with the recent experiment of Bondybey and co-workers. The probability of the formation of the chemisorbed Rh2+C6H6 species, benzene-Rh+, has been discussed in the light of energy calculations.