The potential energy curves and spectroscopic constants of the ground and many excited states of the FrAr van der Waals system have been determined using a one-electron pseudopotential approach. The Fr+ core and the electron–Ar interactions are replaced by effective potentials. The Fr+Ar core–core interaction is incorporated using the accurate CCSD(T) potential of Hickling et al. (Phys. Chem. Chem. Phys. 2004, 6, 4233). This approach reduces the number of active electrons of the FrAr van der Waals system to only one valence electron, which permits the use of very large basis sets for the Fr and Ar atoms. Using this technique, the potential energy curves of the ground and many excited states are calculated at the self consistent field (SCF) level. In addition, the spin–orbit interaction is also considered using the semiempirical scheme for the states dissociating into Fr (7p) and Fr (8p). The FrAr system is not studied previously and its potential interactions, spectroscopic constants and dipole functions are presented here for the first time. Furthermore, we have predicted the X2Σ+–A2Π1/2, X2Σ+–AΠ3/2, X2Σ+–B2Σ1/2+, X2Σ+–32Π1/2, X2Σ+–32Π3/2, and X2Σ+–52Σ1/2+ absorption spectra. © 2012 Wiley Periodicals, Inc.