Quantum mechanics predicts microscopic phenomena with undeniable success. Nevertheless, current theoretical and experimental efforts still do not yield conclusive evidence that there is or is not a fundamental limitation on the possibility to observe quantum phenomena at the macroscopic scale. This question prompted several experimental efforts producing quantum superpositions of large quantum states in light or matter.We report on the observation of quantum correlations, revealed using an entanglement witness, between a single photon and an atomic ensemble of billions of ions frozen in a crystal. The matter part of the state involves the superposition of two macroscopically distinguishable solid-state components composed of several tens of atomic excitations. Assuming the insignificance of the time ordering our experiment indirectly shows lightmatter micro-macro entanglement. Our approach leverages from quantum memory techniques and could be used in other systems to expand the size of quantum superpositions in matter.