Resonance energy transfer (RET) in hybrid polymer/inorganic/organic layers in saponite films, prepared using the ‘layer-by-layer’ (LBL) method, was studied. This method allows the fabrication of a multicomposite molecular assembly based on electrostatic and/or other intermolecular interactions between the interacting species. The LBL films were designed by sequential deposition including positively charged polycations (poly(diallyldimethyl ammonium), PDDA) and negatively charged saponite dispersions with donor molecules (rhodamine 6G) and saponite dispersions with acceptor molecules (rhodamine 3B). In this sequence, the layer of saponite donor molecules was placed on an adjacent layer of saponite acceptor molecules, while the layers were separated by inserting a PDDA polycationic layer. The adsorption process was studied using absorption spectroscopy. The linear deposition regime was completed when ten layers had been deposited. The process of REF was studied by fluorescence spectroscopy. In this case the donor molecules – rhodamine 6G – play the role of light-harvesting antennae and transfer the energy to the next layer covered by energy acceptor, i.e. rhodamine 3B molecules. The insertion of polycation layers is rationalized by the adhesion of negatively charged underlying layers and the stabilization of multicomponent systems. The energy transfer efficiency was affected heavily by changing the distances between the adjacent layers.