Lithium-ion batteries always suffer from serious capability decay, especially when stored at high temperature and/or for prolonged duration. In this work, electrochemical performance for Li-rich layered oxides Li1.20Mn0.54Co0.13Ni0.13O2 was systematically investigated as a function of temperature and duration. Plenty of techniques like SEM, EDS, EIS, ARC, Raman, XRD, and XPS were utilized to characterize the structures, valence states, compositions, particle sizes, and morphologies of the layered oxides with varying temperature and duration. The results reveal that room temperature storage may alter surface kinetics, but hardly influence the electrochemical performance. While in the case of high temperature storage in pristine state, cycling stability is highly dependent on the storage duration. The degradation mechanism at high temperature storage with prolonged duration is demonstrated to be the accumulation of surface species like LiF/Li x PF y O z initiated by the strong reactions between LiPF6 electrolyte and electrode. The results reported here may shed light on predicting electrochemical performance by surface analysis and also provide vital hints on enhancing the high-temperature storage stability of Li-rich layered oxides.