The multicomponent crystals of chloranilic acid (H₂CA) and its alkali salts of monochloranilate trihydrate [RbHCA·0.5H₂CA·3H₂O and CsHCA·0.5H₂CA·3H₂O] and cocrystals with urea [NaHCA·2(NH₂)₂CO and Cs₂CA·(NH₂)₂CO] were prepared and their crystal structures determined. In the crystal structures of RbHCA·0.5H₂CA·3H₂O and CsHCA·0.5H₂CA·3H₂O, molecules of neutral chloranilic acid and its monoanion form stacks of quinoid rings in a face-to-face fashion (the sequence ⋯HCA⁻⋯H₂CA⋯HCA⁻⋯); within the triplet very short centroid–centroid separation distances (<3.30 Å) with the offset of 0.27 Å are observed. In an infinite stack of triplets, interactions between two monoanions are characterised by the centroid–centroid separation distances of ∼3.50 Å and offset of 1.5 Å. The two novel cocrystals with urea reveal anion stacks similar to those of aromatic rings. The Cambridge Structural Database search was used to spot preferences of chloranilic acid and its anions for π-stacking.