An ever-growing demand for high-energy density and high-power Li-ion batteries has driven active research for electrode materials with superior capacity. Recent years have seen the development of Ni-rich transition metal oxide cathode materials due to their high reversible capacity and lower cost. To achieve full capacity from the charge compensation process, a high voltage (>4.4 V) charging is required. However, the battery operation at higher voltages eventually results in dramatic capacity fading and voltage decay with a rapid decomposition of the electrolyte upon further charge-discharge. While previous studies have reported the degradation mechanism within the electrode surface, there have been few empirical investigations into the solid-electrolyte interphase (SEI) formation on Ni-rich cathodes. In the current work, we visualize the different nature of the electrode-electrolyte interphase at various cut-off voltages (2.0-4.2 V, 2.0-4.5 V, and 2.0-4.8 V). We correlate the key properties of the SEI layer with the capacity fading mechanism in the high capacity battery system. The speciation of transition metal elements (Ni, Mn, and Co) into various oxidation and spin states has been identified as the dominant process of the capacity degradation.