The mechanism by which Li additions induce a more homogeneous deformation was systematically investigated in this study by comparing the deformation behavior of pure Mg and Mg-4.5 wt.% Li using experiments, crystal plasticity simulations, and theoretical calculations. The results of the digital image correlation measurements showed that under tension along the transverse direction (TD), strong localized deformation bands with an angle of approximately 20° with respect to the TD were observed in pure Mg, but were absent in Mg-4.5 wt.% Li. Slip trace analyses indicated that basal slip was the predominant deformation mode for pure Mg, whereas that for Mg-4.5 wt.% Li was prismatic slip. A high relative activity of pyramidal 〈c+a〉 slip, approximately 17 %, was observed in Mg-4.5 wt.% Li at a high strain of 10 %. Contraction or double twins were hardly detected during the entire tension process. Crystal plasticity simulations revealed that the 4.5 wt.% Li addition dramatically reduced the critical resolved shear stress (CRSS) ratio of pyramidal 〈c+a〉 slip: prismatic slip: basal slip, which was 31.5:21:1 for pure Mg and 4.3:1.3:1 for Mg-4.5 wt.% Li. Theoretical calculations using the CRSS ratios determined by simulations revealed that easy and uniform deformation propagation induced by a dramatically reduced CRSS ratio of prismatic slip to basal slip played a more important role in improving the deformation homogeneity, in addition to the enhanced activity of pyramidal 〈c+a〉 slip. The mechanisms for how Li additions improve the ductility of Mg are also revisited in this paper.