Metallopolymers incorporating metal ions and polytopic ligands offer the advantage to be easily obtained through a self-assembly process in solution but offer great prospects in the development of multifunctional, smart, even self-healing, materials. We have found that chiral enantiopure ligands containing bis(oxazoline) units in combination with Ni(II) salts generate well-defined thin films either by drop casting or by spin-coating and we demonstrate that the condensation process of these chiral metallosupramolecular assemblies can be characterized through optically active sum-frequency generation.