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Aging-hardening response of Mg-7Al-2Sn (wt%) alloy can be remarkably accelerated by a small addition of silver (Ag). Using high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) coupled with high resolution energy dispersive X-ray spectroscopy (EDS) mapping, for the first time, segregation of solute atoms (Ag in this case) was observed at the interphase boundary between continuous Mg₁₇Al₁₂ precipitate and magnesium matrix in Mg-7Al-2Sn alloy with 0.7 wt% Ag addition. Substantial size refinement and increased number density of Mg₁₇Al₁₂ precipitates may be responsible for the enhanced aging-hardening response in Mg-7Al-2Sn alloy with Ag addition.