Nano/microstructures play an important role in nanoparticle applications. This paper describes an innovative strategy to fabricate a variety of gold nanoparticle aggregates (AuNPs) on large-scale arrays of up to similar to 1 cm(2) made from polystyrene (PS). A dendritic surfactant, C18N3, has multi-amine head groups that can control the thickness of a double layer adsorbed on the PS sphere surface in a pH-dependent manner. Controlling the pH and immersion time in the C18N3 solution allows the morphology of AuNPs deposited on the PS spheres (PS@AuNP) to be regulated. The influence of nano/microstructures on the activity enhancement of glucose oxidase (GOD) was investigated. The results indicated that well-ordered PS@AuNP arrays performed much better in the specific activity enhancement of GOD compared with free GOD and GOD immobilized on PS arrays. Furthermore, it was observed that the immobilized GOD on 2DPS@AuNP arrays maintained a highly improved operational stability compared to free GOD. The mechanism behind this effect is discussed. For practical applications, prepared PS@AuNP arrays can be used as an effective chip for GOD immobilization and application. (C) 2012 Elsevier Inc. All rights reserved.