Film morphology, surface compositions and hydrophobic properties of N-β-aminoethyl-γ- aminopropyl polysiloxane (ASO-1) coated on regenerated cellulose (cel) substrate surface (ASO-1/cel) were investigated and studied by atomic force microscopy, X-ray photoelectron spectroscopy and other techniques. Influenced by the irregularities of cel substrate, ASO-1/cel showed a very similar microscopic morphology to the cel. In addition, the ASO-1/cel surface was hydrophobic. There were strongly hydrogen-bonded linkages at the interface between ASO-1 and cel. All the data indicate that ASO-1 molecules interact with the regenerated cellulose in such a way that the hydrophobic silicon methyl (Si-CH3) groups are oriented towards the air, while the Si—O dipole bonds as well as the polar amino groups are aligned towards the interface of the cellulose substrate.