Biosilicification in diatoms is achieved by specific interactions between silaffins, composed of polypeptides and long-chain polyamines, and silicic acid derivatives. The polycondensation of silicic acids is reported to be catalyzed by the long-chain polyamines that mainly contain tertiary-N-methylpropyleneimine moieties. In this report, we utilized a tertiary amine-containing polymer, poly(2-(dimethylamino)ethyl methacrylate) (poly(DMAEMA)), as a surface-grafted, biomimetic counterpart of the long-chain polyamines in silaffins and demonstrated that the surface-initiated polycondensation of silicic acids, leading to the formation of silica thin films, proceeded smoothly on surfaces presenting poly(DMAEMA), where poly(DMAEMA) was grown from gold surfaces by surface-initiated, atom transfer radical polymerization. The formed silica film was characterized by Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy.