Three two-dimensional (2D) chiral Ag(I) complexes with formulas [Ag4(LR)4(5-nipa)2]n (1), [Ag4(LS)4(5-nipa)2]n (2), and {[Ag4(LS)4(5-hipa)2]·2H2O}n (3) were prepared through the reactions of Ag2O with enantiopure bis-monodentate N-donors (LR/LS) and different dicarboxylic acids bearing A (acceptor)-π-A- and D (donor)-π-A-type structural features, where LR/LS = (-)/(+)-2-(4'-pyridyl)-4,5-pinene-pyridine, 5-H2nipa = 5-nitroisophthalic acid, and 5-H2hipa = 5-hydroxyisophthalic acid. A study of their nonlinear optical responses reveals that chiral 1 and 2 enantiomeric pairs with the A-π-A-type dicarboxylic acid ligand simultaneously display second- and third-harmonic generation (SHG and THG) responses, while chiral 3 containing the D-π-A-type dicarboxylic acid ligand only exhibits a very strong THG response. The THG intensity of 3 is 451 × α-SiO2, being about 27 and 24 times larger than those of 1 and 2, respectively.