Lots of charmonium-like structures have been observed in the last two decades. Most of them have quantum numbers that can be formed by a pair of charm and anticharm quarks, thus it is difficult to unambiguously identify the exotic ones among them. In this Letter, by exploiting heavy quark spin symmetry, we present a robust prediction of the hadronic molecular scenario, where the ψ(4230), ψ(4360) and ψ(4415) are identified as DD[over ¯]_{1}, D^{*}D[over ¯]_{1}, and D^{*}D[over ¯]_{2}^{*} bound states, respectively. We show that a flavor-neutral charmonium-like exotic state with quantum numbers J^{PC}=0^{--}, denoted as ψ_{0}(4360), should exist as a D^{*}D[over ¯]_{1} bound state. The mass and width of the ψ_{0}(4360) are predicted to be (4366±18) MeV and less than 10 MeV, respectively. The ψ_{0}(4360) is significant in two folds: no 0^{--} hadron has been observed so far, and a study of this state will enlighten the understanding of the mysterious vector mesons between 4.2 and 4.5 GeV, as well as the nature of previously observed exotic Z_{c} and P_{c} states. We propose that such an exotic state can be searched for in e^{+}e^{-}→ηψ_{0}(4360) and uniquely identified by measuring the angular distribution of the outgoing η meson.