Si/N-doped TiO2 core/shell nanopillar arrays with a nanoporous structure are fabricated through a simple protein-mediated TiO2 deposition process. The Si nanopillar arrays are used as templates and alternatively immersed in aqueous solutions of catalytic molecules (protamine, PA) and the titania precursor (titanium(IV) bis(ammonium lactato)dihydroxide, Ti-BALDH) for the layer by layer mineralization of a PA/TiO2 coating. After a subsequent calcination, a N-doped TiO2 layer is formed, and its thickness could be controlled by varying the cycles of deposition. Moreover, the nanoporous structure of the Si nanopillars strongly affects the formation of the TiO2 layer. The obtained Si/TiO2 nanocomposites show significantly improved solar absorption compared with commercially purchased TiO2 nanoparticles.