Abstract: Practical use of lithium (Li) metal for high–energy density lithium metal batteries has been prevented by the continuous formation of Li dendrites, electrochemically isolated Li metal, and the irreversible formation of solid electrolyte interphases (SEIs). Differentiating and quantifying these inactive Li species are key to understand the failure mode. Here, using operando nuclear magnetic resonance (NMR) spectroscopy together with ex situ titration gas chromatography (TGC) and mass spectrometry titration (MST) techniques, we established a solid foundation for quantifying the evolution of dead Li metal and SEI separately. The existence of LiH is identified, which causes deviation in the quantification results of dead Li metal obtained by these three techniques. The formation of inactive Li under various operating conditions has been studied quantitatively, which revealed a general “two-stage” failure process for the Li metal. The combined techniques presented here establish a benchmark to unravel the complex failure mechanism of Li metal.