Silver-based I-III-VI-type semiconductor nanocrystals have received extensive attention due to their narrow-band luminescence properties. Herein, we demonstrated a seed-mediated growth of quaternary Ag-In-Ga-S (AIGS) nanocrystals (NCs) with narrow-band luminescence. By conducting partial cation exchange with In3+ and Ga3+ based on Ag2S NCs and controlling the Ag/In feeding ratios (0.25 to 2) of Ag-In-S seeds as well as the inventory of 1-dodecanethiol, we achieved optimized luminescence performance in the synthesized AIGS NCs, characterized by a narrow full width at half maximum of less than 40 nm. Meanwhile, narrow-band luminescent AIGS NCs exhibit a tetragonal AgGaS2 crystal structure and a gradient alloy structure, rather than a core-shell structure. Most importantly, the kinetics decay curves of time-resolved photoluminescence and the ground state bleaching in transient absorption generally agree with each other regarding the lifetime of the second decay component, which indicates that the narrow-band luminescence is due to the slow radiative recombination between trapped electrons and trapped holes located at the edge of the conduction band and the deep silver-related trap states (e.g., silver vacancy), respectively. This study provides new insights into the correlation between the narrow-band luminescence properties and the structural characteristics of AIGS NCs.