Thanks to the 119Sn Mössbauer hyperfine parameters, it is possible to analyze and predict Li reaction mechanisms with Sn-based negative electrodes for Li-ion batteries. The present approach is based on the interpretation of the 119Sn Mössbauer hyperfine parameters: isomer shift (δ) and quadrupole splitting (Δ) by considering: (i) the analysis of the 119Sn Mössbauer hyperfine parameters of the Li–Sn alloys used as model compounds, (ii) their interpretation from some physicochemical parameters (Li/Sn ratio, crystal structure, electronic density as defined by Hume-Rothery), and (iii) the proposition of an experimental based model to understand Li lithiation/delithiation mechanisms and predict electrochemical performances for Sn-based compounds including the effects of volume variations, particle coalescence or SEI formation.