A hybrid system of mesoporous silica (MS) particle incorporated with poly(amidoamine) dendrimer-encapsulated platinum nanoparticles (Pt-DENs) was constructed in a neutral aqueous solution through electrostatic interaction. The MS/Pt-DENs composite particles immobilized with glucose oxidase (GOx) were used to modify a glassy carbon electrode for detecting the electrocatalytic response to the reduction of glucose. Pt-DENs can improve the conductivity of MS and enhance the electron transfer between redox centers in enzymes and electrode surfaces. The structure of composite particles and the performance of MS/Pt-DEN-modified electrodes were characterized by transmission electron microscopy, N2 sorption characterization method, electrochemical impedance spectroscopy, cyclic voltammetry and amperometric measurements. The MS/Pt-DENs/GOx-modified electrodes, which had a fast response of GOx less than 3 s, could be used for the determination of glucose ranging from 0.02 to 10 mM. The detection limits were 4 μM at signal-to-noise ratio of 3.