Electrons in image-potential states on the surface of bulk helium represent a unique model system of a two-dimensional electron gas. Here, we investigate their properties in the extreme case of reduced film thickness: a monolayer of helium physisorbed on a single-crystalline (111)-oriented Cu surface. For this purpose we have utilized a customized setup for time-resolved two-photon photoemission (2PPE) at very low temperatures under ultra-high vacuum conditions. We demonstrate that the highly polarizable metal substrate increases the binding energy of the first (n = 1) image-potential state by more than two orders of magnitude as compared to the surface of liquid helium. An electron in this state is still strongly decoupled from the metal surface due to the large negative electron affinity of helium and we find that even one monolayer of helium increases its lifetime by one order of magnitude compared to the bare Cu(111) surface. [4,7, 8] with Fermi temperatures in the mK range, and spacing of the excited states in the microwave regime [9]. For electrons on the bulk surface of He, the maximum density is small: for more than ≈ 2 × 10 9 electrons per cm −2 the layer becomes unstable [10] and the electron gas remains in the classical regime. Early, it was realized that the density of such electron layers can be significantly increased by growing He films of finite thickness on top of a substrate with large permittivity [11,12]. For a 100Å He film on a doped silicon substrate, for example, densities of up to 10 11 cm −2 have been reported [13]. Such densities offer the possibility to study the quantum regime of this almost ideal 2D electron system including effects as Wigner crystallization and quantum-melting [12] as long as the electron gas is well decoupled from the substrate. For very thin films, however, the coupling to the substrate will be strongly influenced by surface roughness and impurities of the substrate which can lead to lateral localization and enhanced tunneling through the film [13,14]. The study of this regime thus requires the combination of advanced surface science and cryogenic techniques.In this Letter, we investigate the limiting case of a monolayer (ML) of He on an atomically flat singlecrystalline metal substrate and present a study of the electron transfer dynamics of the image-potential states on this archetypical 2D system. Image potential states on clean and rare gas covered metal surfaces already proved to be ideal model systems for the electron transfer dynamics at surfaces and through thin dielectric layers, by theory and by experiment, in particular by two-photon photoemission (2PPE) studies [15]. For thin films of the heavier rare gases, it has been shown that the coupling of the image-potential states to the metal strongly depends on the electron affinity of the film which represents a tunnel barrier in the case of negative electron affinity [6,[16][17][18]. He films are expected to exhibit a particular high barrier (the electron affinity of condensed He is −1.3 eV [19]), which ...