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Intense laser-produced plasma is a complex amalgam of ions, electrons and atoms both in ground and excited states. Little is known about the spatial composition of the excited states that are an integral part of most gaseous or cluster plasma. In cluster-plasma, Rydberg excitations change the charge composition of the ions through charge transfer reactions and shape the angular distributions. Here, we demonstrate a non-invasive technique that reveals the anisotropic Rydberg excited cluster sheath by measuring anisotropy in fast neutral atoms. The sheath is stronger in the direction of light polarization and the enhanced charge transfer by the excited clusters results in larger neutralization.