Energy relaxation processes of photo-excited Kr-(50) over bar clusters covered with a shell of Ar atoms (up to 40), which are embedded inside large Ne-(7500) over bar clusters are investigated with energy resolved fluorescence spectroscopy. In the energy range of the characteristic Ne cluster absorption (16.5-18 eV) a strong energy transfer to the embedded Kr cluster is observed, which results in the desorption of electronically excited Kr-* atoms. Kr-* atoms move through the Ne cluster, desorb and emit visible and near-infrared light in the vacuum (5p-->5s). By coating the Kr clusters with Ar atoms, the Kr lines disappear and 4p-->4s transitions of Ar-* become dominant. Additionally, new emission bands occur, which are assigned to transitions of perturbed atomic Kr 5p-states inside Ne clusters. Due to the interaction of electronically excited Kr-* atoms with neutral Ar atoms in the surrounding shell, several excited Kr states namely 5p [1/2](0) and 5p [3/2](2) decay nonradiatively. This is in agreement with the well-known "energy-gap law." The results give experimental evidence that clusters with a multishell structure can be prepared by a sequential pick-up technique. This allows the preparation of Kr clusters embedded inside Ne clusters and coated with a shell of Ar atoms. Such clusters cannot be prepared with conventional coexpansion techniques. (C) 2003 American Institute of Physics.