Biomimetic synthesis of shaped functional inorganic materials is still a hot issue. In this work, we investigated the influence of crystallization conditions on formation of crystalline aggregates from comb-like polyethyleneimine (cPEI). A range of well-controlled polymeric aggregates rich in basic amine groups were prepared through a crystallization-driven self-assembly of cPEI under varied conditions such as different crystallization media (including solvent type and composition) and temperature, as well as the presence of metal cations of different valence. Meanwhile, these crystalline aggregates were applied as catalytic templates to replicate silica with corresponding structures and shapes. The cPEI templates and the templated silica products were mainly subjected to scanning electron microscope (SEM) observation, Fourier transform infrared (FT-IR) and X-ray diffraction (XRD) measurements. The results indicated that cPEI was a very effective template component for the construction of specially structured silica materials being due to the special crystallites growing behavior of cPEI. (C) 2016 Elsevier Ltd. All rights reserved.