We synthesized a highly ordered mesoporous silica coating on polyamide (PA) by adding PA powder to the solution of silica precursors in different pH conditions. A pH equal to 7.0 and 8.0 afforded PA coated with spherical silica particles with an average diameter of 112 and 70 nm, respectively; a pH higher than 9.0 furnished a 150-nm thick coating consisting of hexagonally ordered mesostructured pores. The silica-coated PA samples presented lower melting points compared with the neat PA and are potentially applicable in many research fields such as rapid prototyping technology.