The early reported pseudo-first-order reaction kinetics of the polymer-supported metallic nanocatalysts for the model reaction of p-nitrophenol (p-NP)/NaBH4 were probably oversimplified. Here a detailed study of p-NP reduction by NaBH4 in the presence of the raspberry-like poly(allylamine hydrochloride)-modified polymer poly(glycidyl methacrylate) composite sub-microspheres with tunable gold nanoparticles (PGMA@PAH@AuNPs) was presented. Effects of polyelectrolyte concentration, the ratio of polymer spheres to gold nanoparticles, and the solution pH value for composite synthesis on the induction period, reaction time, average reaction rate and average turnover frequency were systematically investigated. Experimental results in all cases of our study revealed an n(th) order (n > 1) of the p-NP/NaBH4 catalytic reaction by the prepared polymer composite particles. The apparent order of reaction, n, is dependent on the total surface area of the coated gold nanoparticles on the polymer spheres, which can be closely correlated with the tunable gold nanoparticle surface coverage. The mechanism of the observed catalytic activity enhancement was proposed based on active epoxy groups of the polymer spheres and a large adsorption of p-nitrophenolate anions onto the positively-charged spheres.