Quantum systems unfold diversified correlations which have no classical counterparts. These quantum correlations have various different facets. Quantum entanglement, as the most well known measure of quantum correlations, plays essential roles in quantum information processing. However, it has recently been pointed out that quantum entanglement cannot describe all the nonclassicality in the correlations. Thus the study of quantum correlations in separable states attracts widely attentions. Herein, we experimentally investigate the quantum correlations of separable thermal states in terms of quantum discord. The sudden change of quantum discord is observed, which captures ambiguously the critical point associated with the behavior of Hamiltonian. Our results display the potential applications of quantum correlations in studying the fundamental properties of quantum system, such as quantum criticality of non-zero temperature.