Pulmonary surfactant, which is a complex mixture of lipids and proteins, plays a key role in the functional properties of the respiratory system. Lipids form complexes with proteins to maintain low values of surface tension at continuous compression/expansion deformations. However, interactions that lead to the complexation still remain to be unknown thus significantly hampering the development of synthetic analogs of the natural pulmonary surfactant. In this work, the methods of surface rheology and ellipsometry have been employed to study the dynamic properties of model phospholipid monolayers applied onto the surfaces of synthetic polyelectrolyte solutions. It has been shown, that electrostatic or hydrophobic interactions between lipids and macromolecules are insufficient for the efficient complexation and maintenance of low surface tension values.