Materials based on ureidopyrimidinone (UPY) dimers and Adenine (A) / Thymine (T) derivatives were synthesized and characterized by advanced solid state NMR (Nuclear Magnetic Resonance) techniques. Silylated UPY molecules were used as model compounds, leading to structured organic-inorganic materials after hydrolysis and condensation processes (sol-gel reactions). High resolution 1H solid state NMR has been extensively used for the in-depth description of the H-bond networks, including very fast MAS (Magic Angle Spinning) experiments at very high field and DQ (double quantum) recoupling experiments. The chemical nature of the organic-inorganic interface has been illuminated by such techniques. In, particular, it has been demonstrated that H-bond networks were preserved during sol-gel reactions and were comparable to those observed in the UPY crystalline precursors.