The gas phase structures of anisole dimer in the ground and first singlet electronic excited states have been characterized by a combined experimental and computational study. The dimer, formed in a molecular beam, has been Studied by resonance-enhanced multiphoton ionization and high-resolution laser-induced fluorescence techniques. The assignment of the rotational fine structure of the S-1 <- S-0 electronic transition origin has provided important Structural information on the parallel orientation of aromatic rings of anisole moieties. By comparison with the DFT/TD-DFT computational results, it has been possible to infer the detailed equilibrium Structure of the complex. The analysis of the equilibrium structure and interaction energy confirms that the anisole dimer is stabilized by dispersive interaction in the gas phase. This is, to the best of our knowledge, the first detailed work (reporting both theoretical and high-resolution experimental data) on an isolated cluster in the pi-stacking configuration.