Herein, we report on the ability to create complex 2-D and 3-D silica networks in vitro via polycationic peptide-mediated biosilicification under experimentally altered chemical and physical influences. These structures differ from the sphere-like silica network of particles obtained in vitro under static conditions. Under chemical influences, overall morphologies were observed to shift from a characteristic network of sphere-like silica particles to a sheetlike structure in the presence of −OH groups from additives and to sharp-edged, platelike structures in the presence of larger polycationic peptide matrixes. Under physical influences, using externally applied force fields, overall silica morphologies were observed to transition from sphere-like to fiberlike and dendrite-like structures. These findings could lead to the future development of bio-inspired complex 2-D and 3-D silica micro- and nano-devices.