Four coordination polymers, [CsL1(H2O)2]·H2O (1), [CsL2(H2O)2]·H2O (2), [Rb2(L2)2(H2O)2]·2H2O (3) and [RbL3(H2O)] (4), were synthesized by Cs(I), Rb(I) and 4′-hydroxyisoflavone-3′-sulfonates L1–L3 [L1 = 7-methoxy-4′-hydroxyisoflavone-3′-sulfonate, L2 = 7-ethoxy-4′-hydroxyisoflavone-3′-sulfonate, L3 = 7-ethoxy-4′,5-dihydroxyisoflavone-3′-sulfonate]. The crystal structures of 1–4 were determined by single-crystal X-ray diffraction. The influences of 4′-hydroxyisoflavone-3′-sulfonate ligands and Cs+, Rb+ on their structural features and self-assembly were investigated. The sulfonates of L1–L3 not only coordinate with Cs+ or Rb+ directly, but also bridge the organic region and the inorganic region in 1–4. Non-covalent interactions such as coordination interaction, π–π stacking interaction and hydrogen bonding assembled 1–4 into 3-D networks together with the electrostatic interactions between Cs+, Rb+ and the sulfonate anions.