Long-range metastable molecules consisting of two cesium atoms in high Rydberg states have been observed in an ultracold gas. A sequential three-photon two-color photoassociation scheme was employed to form these molecules in states, which correlate to np(n + 1)s dissociation asymptotes. Spectral signatures of bound molecular states are clearly resolved at the positions of avoided crossings between long-range van der Waals potential curves. The experimental results are in agreement with simulations based on a detailed model of the long-range multipole-multipole interactions of Rydbergatom pair states. We show that a full model is required to accurately predict the occurrence of bound Rydberg macrodimers. The macrodimers are distinguished from repulsive molecular states by their behavior with respect to spontaneous ionization and possible decay channels are discussed.A new regime of ultracold chemistry has been established by the possibility to routinely produce ultracold atomic samples with translational temperatures below 1 mK using laser cooling [1,2] and trapping [3,4]. The characteristic feature of this regime is that reactions are not driven by thermodynamical quantities, i.e. temperature or pressure, but by the precise manipulation of the internal quantum states of the constituents and the interactions between them. Landmark results in the emerging field of ultracold chemistry include the formation of ultracold molecules in the absolute ground state using photoassociation [5][6][7] or magneto-association [8,9], the control of chemical reactions by manipulating the quantum statistics of the reactants [10,11], or the photodissociation of molecules with full control over reactant and product channels [12]. The enabling factor in all these studies is the control of long-range interaction potentials, which dominate the dynamics at low collision energies.An extreme case of long-range interactions are van der Waals forces between two atoms in Rydberg states, scaling in the case of an off-resonant dipole-dipole interaction with the internuclear separation R as R −6 and with the principal quantum number n as n 11 [13]. Metastable molecular states with internuclear separations exceeding 1 µm, so called macrodimers, are predicted to result from these interactions [14][15][16]. The molecular potential minima supporting these bound states arise from avoided crossings between long-range potential-energy curves correlating to different dissociation asymptotes of the doubly-excited dimers (see Fig. 1). Astonishingly, such macrodimers are predicted to have lifetimes limited by radiative decay of the constituent atomic Rydberg states [17], even though they are energetically located in the Cs + Cs + + e − ionization continuum and the density of electronic states is extremely high, two conditions one would expect to lead to fast autoionization [18]. Experimentally, these molecular states have remained elusive. Molecular resonances were observed in the Rydberg-excitation spectrum of ultracold gases and were identified as arisi...