Geometries and interaction energies of benzene complexes with pyridine, pyridinium, N-methylpyridinium were studied by ab initio molecular orbital calculations. Estimated CCSD(T) interaction energies of the complexes at the basis set limit were -3.04, -14.77, and -9.36 kcal/mol, respectively. The interactions in the pyridinium and N-methylpyridinium complexes should be categorized into a cation/pi interaction, because the electrostatic and induction interactions greatly contribute to the attraction. On the other hand, the interaction in the pyridine complex is a pi/pi interaction. The dispersion interaction is mainly responsible for the attraction in the benzene-pyridine complex. Short-range interactions including charge-transfer interactions are not important for the attraction in the three complexes. The most stable pyridinium complex has a T-shaped structure, in which the N-H bond points toward the benzene, while the N-methylpyridinium complex prefers a slipped-parallel structure. The benzene-pyridine complex has two nearly isoenergetic (Slipped-parallel and T-shaped) structures.