This study demonstrates a method for synthesis of amine functionalized and easily size controllable silica nanoparticles through biomimetic polyamine complex. First, we generate a polyamine nanocomplex composed of polyallylamine hydrochloride (PAH) and phosphate ion (pi) to synthesize silica nanoparticles. The size of polyamine nanocomplex is reversibly adjusted within the range of about 50 to 300 nm according to the pH conditions. Amine groups of the PAH in the nanocomplex catalyzes the condensation reaction of silicic acid. As a results, silica nanoparticles are synthesized based on nanocomplex in a very short time. Finally, we synthesize silica nanoparticles with various sizes according to the pH conditions. In the process of synthesizing silica nanoparticles, polyamine chains that act as catalysts are incorporated into the inside and surface of the particles, subsequently, amine groups are exposed on the surface of silica nanoparticles. As a results, the synthesis and surface modification of silica nanoparticles are performed simultaneously, and the silica nanoparticles introduced with amine groups can be easily synthesized by adjusting the sizes of the silica nanoparticles. Finally, we demonstrate the synthesis of functional silica nanoparticles in a short time under milder conditions than the conventional synthetic method. Furthermore, this method can be applicable to bioengineering and materials fields.