A new nanocomposite of poly(o-methoxyaniline) (POMA) is introduced by overlayer formation of POMA on silica.The key appealing feature of the synthesis is the role of silica sulfuric acid (SSA) both as solid acid dopant and template in overlayer self-assembly of POMA on silica surface. Hereon siloxide group (Si-O À ) of silica surface is replaced with dopant anion of SSA (≡Si-O-SO 3 À ), which leads to formation of a overlayer of POMA on the silica surface. The composite particles are spherical in the nanoscale range of 50 nm without application of any external template (notemplate synthesis). Nanocomposite was fully characterized by various instrumentation methods: Fourier transform infrared (FT-IR), ultraviolet-visible (UV-vis), thermogravimetric analysis (TGA), diffrential thermal analysis (DTA), elemental analysis (CHNS), energy dispersive X-ray (EDX), X-ray photoelectron spectroscopy (XPS) and X-ray difraction (XRD). Based on XPS and CHNS results, it is demonstrated that the doping level of POMA is as high as 50% and for the first time the ratio of 4:2:2 is obtained for -NH-(amine): -HN .+ -(polarons): ¼HN + -(bipolarons), respectively. In fact, bipolarons may also coexist with polarons with a 1:1 ratio of them. Moreover, the synthesis benefits from the perspective of green chemistry which is preparation under solid-state (solvent-free) condition.