An experimental spectroscopic study of the van der Waals aniline-Ar-n, clusters (n = 1-6) has been achieved via resonant two-photon two-color ionization, whose results improve the accuracy of the previously reported spectra and complete them by the observation of further structure in the spectra of well-defined structural isomers. These experimental results have been analyzed in detail in relation with molecular dynamics simulations including minimum energy structures calculations, direct spectral simulations, and isomerization dynamics. Two potential energy surfaces, in both the ground S-0 and the electronically excited SI states, have been built in order to recover the main experimental observables. They permit the site specific electronic shift additivity rule to be confirmed by the semiclassical spectral simulations and a global picture of the solvation phenomena in this aromatic-rare gas atom system to be provided, In particular, careful examination of the isomerization dynamics helps the general understanding of the structural behavior of these microsolvent clusters.