The electronic structure of supported mass-selected Ag3 clusters is analyzed by joint femtosecond photoemission spectroscopy and ab initio theoretical investigations. A wide band gap insulating magnesia ultra-thin film on Mo(100) has been chosen as substrate in order to minimize the electronic interaction between metal clusters and support. After magnesia ultra-thin film preparation no photoemission from the molybdenum substrate is observed anymore, instead very weak two photon photoemission is detected possibly originating from surface or subsurface oxide defect states. Soft-landing deposition of 2\({\%}\) of atomic monolayer equivalents of Ag3 clusters results in the disappearance also of the MgO two photon photoemission signal, while a strong single photon photoemission signal is detected from states located directly below the Fermi level. The theoretical study of structural, electronic and optical properties of Ag3 at two model sites of MgO (100), the stoichiometric MgO(100) and an FS-center defect, based on the DFT method and the embedded cluster model provides insight into the interactions between the cluster and the support which are responsible for the characteristic spectroscopic features.