When agricultural residues are processed to ethanol, lignin and silica are some of the main byproducts. Separation of these two products is difficult and the chemical interactions between lignin and silica are not well described. In the present study, the effect of lignin-silica complexing has been investigated by characterizing lignin and silica coprecipitates by FTIR and solid state NMR. Silica particles were coprecipitated with three different lignins, three lignin model compounds, and two silanes representing silica-in-lignin model compounds. Comparison of ²⁹Si SP/MAS NMR spectra revealed differences in the distribution of silanol hydroxyl groups among different coprecipitates. These differences are dependent on the lignin type. The results are interpreted that the underlying mechanism of the interactions is the formation of hydrogen bonds between lignin aliphatic hydroxyl or carboxyl groups and the silanols, but not a condensation of the silica-in-lignin among the silica particles and not the formation of C-O-Si bonds.