Ten organic molecule models simulating the chemical functions of commercial superplasticizers used in the cement/concrete industry were intercalated into lamellar calcium aluminate hydrates to synthesize hybrid AFm phases. AFm phases, encountered in cement hydration chemistry, belong to the large Layered Double Hydroxide (LDH) family. The intercalation process was performed using the anion exchange method. The affinities of the model molecules toward the AFm mineral layers, [Ca2Al(OH)6]+, were compared using several complementary techniques. They display the following tendencies: –PO32− > –SO3− > –CO2− for the hydrophilic parts and heptyl-R > phenyl-R > pentyl-R > ethyl-R for the hydrophobic parts. The organic-inorganic interface of the hybrid AFm phases was achieved. The organic molecule arrangement is either perpendicular or parallel to the inorganic main layer, resulting in various connection modes, from intercalation to grafting. The results enable a better understanding of the chemical reactivity of the utilized superplasticizers during the concrete setting process.