Sub-Doppler electronic spectra with hundreds of resolved rotational lines are now available for benzene-Ar dimers and trimers. From their analysis the structure of these clusters is precisely determined. The analysis of two bands, 6 0 1 and 16 0 2 , of C6H6 · Ar is presented in detail. It leads to accurate values of the van der Waals bond length in the electronic ground and excited state. The change in frequency upon clustering is found to be a factor of 17 larger for the overtone of the out-of-plane modev 16 than for the in-plane vibrationv 1. This can be tentatively explained by an interaction of the low frequency out-of-plane motion of the ring with the van-der-Waals motion of the Ar atom.