From the reactions between 2,5-(dianilino)terephthalic acid and Li2CO3 or MgIJOH)2 in water, three new layered compounds were prepared. The corresponding structures were determined by single crystal X-ray diffraction studies. Depending on the experimental conditions, two polymorphs can be obtained when using Li2CO3 as base namely [(LiIJOH2)3)2IJC20H14N2O4)]·2H2O (Ia) and [(LiIJOH2)4)2IJC20H14N2O4)] (Ib). Compound Ia (form α) crystallizes in the P1¯ space group with lattice parameters a = 7.4372(6) Å, b = 8.2866(5) Å, c = 10.6200IJ13) Å, α = 98.674IJ7)°, β = 107.377IJ14)°, and γ = 90.655IJ6)°, whereas compound Ib (form β) adopts the P21/c space group with cell parameters a = 11.955(2) Å, b = 6.2885(4) Å, c = 16.030(2) Å, and β = 91.726IJ12)°. The neutralization reaction with MgIJOH)2 leads to the formation of [MgIJOH2)6IJC20H14N2O4)]·2.8H2O (II), which crystallizes in the P1¯ space group with lattice parameters a = 13.6558IJ19) Å, b = 15.903(3) Å, c = 16.6894IJ10) Å, α = 94.295IJ11)°, β = 113.23IJ1)°, and γ = 110.377IJ11)°. All these structures can be systematically described by the stacking of alternating bi-layers as previously reported with the sodiated counterpart. One layer consists of 2,5-(dianilino)terephthalate dianions (C20H14N2O42−) while the other is composed of the corresponding cations (Li+ or Mg2+) coordinated by water molecules. The distance between the two layers depends on the nature of the cation and its coordination as well as the conformation of the organic anion. Such original 2-D host lattices appear quite interesting as anion-inserting electrode materials for promoting the emerging field of p-type rechargeable organic batteries.