Abstract. Interactions of adenosine 3':5'-cyclic monophosphate (cAMP) and N 6 ,2'-O-dibutyryladenosine 3':5'-cyclic monophosphate (dbcAMP) with a lipid layer composed of monoolein-based preparation and dioleoyl phosphatidylcholine (DOPC) were investigated by small-angle X-ray diffraction (SAXD) and Raman spectroscopy. The reversed hexagonal (H II ) MO/DOPC/H 2 O phase of 65:15:20 wt.% composition was selected as a reference system. SAXD revealed that entrapment (at the expense of water) of 3 wt.% cAMP into the reference system did not change the polymorphic form and structural parameters of the phase. The same content of dbcAMP induced the transition from the H II phase to the reversed bicontinuous cubic phase of space group Ia3d. This transition is explained by the increase of lipid head-group area due to the penetration of the acylated adenine group of dbcAMP into the polar/apolar region of lipid layer. The conclusion is supported by Raman spectroscopy, showing the disruption/weakening of hydrogen bonding in the MO/DOPC-based matrix at the N1-and N3-sites of the dbcAMP adenine ring. As distinct from dbcAMP, cAMP remains mostly in the water channels of the H II phase, although the phosphate residue of nucleotide interacts with the quaternary ammonium group of DOPC. Both nucleotides increase the population of gauche isomers in the DOPC choline group.