A bridged silsesquioxane was obtained from a monosilylated precursor derivative of ureidopyrimidinone, which combines self-assembling properties and hydrophobic interaction of a long alkyl linker (10 carbons). The formation of the organic bridge was promoted through dimerisation via the 4 H-bonds of the ureidopyrimidinone functionality. The association of the organic bridge was brought by the hydrophobic interactions of the long alkylene chains between the organic bridges and the terminal hydrolysable trialkoxysilyl functionality. The self-assembling and structuring of the molecular precursor was transcribed to the resulting hybrid bridged silsesquioxanes after hydrolysis–condensation in aqueous acidic conditions as shown by a set of spectroscopic methods. The long hydrocarbon chain greatly influences the structuring and the morphology of the hybrid material.