Layer formation and annealing of nanoparticles especially colloidal inks applied to porous materials is very relevant for functional coatings and printing. The goal is to distinguish and quantify the differences in structure formation during annealing of deposited colloidal inks on a porous and a solid material. Therefore, we compare two different substrates: As porous template we use a layer of cellulose nano fibers (CNF) – so-called nanopaper – and as non-porous reference medium silicon. We use novel colloidal inks consisting of poly-butylmethacrylate (PBMA) and poly-sobrerolmethacrylate (PSobMA) in aqueous solution. We studied the deposition and the subsequent structural and morphological changes during annealing of the colloidal layers in real-time. We use grazing incidence small-angle neutron scattering (GISANS) and grazing incidence small-angle X-ray scattering (GISAXS). During deposition part of the liquid enters the CNF layer while part of the solvent and the colloids remain on top of the nanopaper surface, leading to a complex drying process. Our results show that the CNF- and colloidal layer will change if the glass transition temperature of the colloids is exceeded.