Discovery of new high-conductivity solid-state ionic conductors has been a long-lasting interest in the field of solid-state ionics for their important applications in solid-state electrochemical devices. Here, we report the mixed oxide-ion and Li-ion conductions, together with their conducting mechanisms in the Li2W2O7 material with triclinic symmetry. The process for the ionic identity is supported by several electrochemical measurements including electrochemical impedance spectroscopy, DC polarization, oxygen concentration cell, and theoretical analysis of neutron diffraction data and bond-valence-based energy landscape calculations. We show from electrochemical measurements strong evidences of the predominating oxide-ion conducting and minor Li-ion chemistry in Li2W2O7 at high temperatures, while the bond-valence-based energy landscape analysis reveals possible multidimensional ionic migration pathways for both oxide-ions and Li-ions. Thus, the presented results provide fundamental insights into new mixed ionic conduction mechanisms in low-symmetry materials and have implications for discoveries of new ionic conductors in years to come.