Complexes like the studied DNA and didecyldimethylammonium chloride are promising materials for organic electronics and photonics. Water content in this material as the solid state is a key factor for its electronics properties and microstructure. DNA complex was subjected to controlled hydration from gaseous phase and next studied by 1H-nuclear magnetic resonance spectroscopy. Variations of spin-spin and spin-lattice relaxation times as a function of hydration level are reported. Formation of tightly and loosely bound water fractions at rehydration process is discussed.